Fluorinating agent and fluorinating method

Abstract

The present invention provides a fluorinating agent that can be manufactured by a simple method, and a fluorinating method using the fluorinating agent that can be manufactured by a simple method. [Solution] A fluorinating agent containing a fluorine-containing compound and fluoride ions.

Description

Technical Field

[0001] The present disclosure relates to a fluorinating agent and a fluorination method.

Background Art

[0002] Potassium fluoride (KF) is known as a fluorinating agent such as organic chloride. Potassium fluoride is usually synthesized by the reaction of HF and KOH, and processed into fine powder by a spray drying method (see, for example, Non-Patent Document 1).

Prior Art Documents

Non-Patent Documents

[0003]

Non-Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] Conventionally, potassium fluoride known as a fluorinating agent has a problem that it uses strong acid and strong base, and further needs to be made into fine powder by a spray drying method, resulting in a complicated manufacturing process.

[0005] An object of the present disclosure is to provide a fluorinating agent that can be produced by a simple method, and a fluorination method using the fluorinating agent that can be produced by a simple method.

Means for Solving the Problems

[0006] The present disclosure (1) is a fluorinating agent containing a fluorine-containing compound and fluoride ions.

[0007] The present disclosure (2) is the fluorinating agent according to the present disclosure (1) which is solid at 25°C.

[0008] The present disclosure (3) is such that the counter ion of the fluoride ion is an alkali metal, an alkaline earth metal, and NR

[0013] , 4 (R 1 may be the same or different and is at least one selected from the group consisting of H or an organic group having 1 to 10 carbon atoms), and is the fluorinating agent according to the present disclosure (1) or (2).

[0009] The present disclosure (4) is a fluorinating agent in any combination with any one of the present disclosures (1) to (3) further containing a base.

[0010] The present disclosure (5) is the fluorinating agent according to the present disclosure (4) wherein the base is a solid at 25°C.

[0011] The present disclosure (6) is the fluorinating agent according to the present disclosure (4) or (5) wherein the pKa of the base is 8 to 40.

[0012] The present disclosure (7) is such that the base is R 10 OM (wherein R 10 is H or an organic group having 1 to 10 carbon atoms, M is a metal or NR 1 4 (R 1 may be the same or different and is H or an organic group having 1 to 10 carbon atoms).), and is a fluorinating agent in any combination with any one of the present disclosures (4) to (6) which is at least one selected from the group consisting of the compound represented thereby and a metal carbonate.

[0013] The present disclosure (8) is a fluorinating agent in any combination with any one of the present disclosures (4) to (7) wherein the base is at least one selected from the group consisting of sodium hydroxide, potassium hydroxide, cesium hydroxide, cesium carbonate, sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide, sodium t-butoxide, and potassium t-butoxide.

[0014] The present disclosure (9) is a fluorinating agent in any combination with any one of the present disclosures (4) to (8) wherein the content of the base is 0.1 to 70% by mass.

[0015] Disclosure (10) is a fluorinating agent in any combination with any of Disclosures (1) to (9), wherein the fluorine-containing compound is solid at 25°C.

[0016] Disclosure (11) is a fluorinating agent in any combination of the fluorine-containing compound with any of Disclosures (1) to (10), wherein the fluorine-containing compound is a fluorine-containing polymer.

[0017] Disclosure (12) is a fluorinating agent in any combination of any of Disclosures (1) to (11), wherein the fluorine-containing compound is a fluorine-containing polymer comprising a polymerization unit based on at least one monomer selected from the group consisting of tetrafluoroethylene, difluoroethylene, chlorotrifluoroethylene, hexafluoropropylene, perfluoro(alkyl vinyl ether), trifluoroethylene, and monofluoroethylene.

[0018] Disclosure (13) is a fluorinating agent in any combination with any of Disclosures (1) to (12), wherein the fluorine-containing compound is at least one selected from the group consisting of polytetrafluoroethylene, polyvinylidene fluoride, and polychlorotrifluoroethylene.

[0019] This disclosure (14) is a fluorinating agent which is a composition obtained by mechanochemical treatment of a fluorine-containing compound and a base.

[0020] This disclosure (15) is a fluorination method that includes a step of fluorinating an object using the fluorinating agent described in this disclosure (14).

[0021] This disclosure (16) is a fluorination method that includes a step of fluorinating an object using a fluorinating agent containing a fluorine-containing compound and fluoride ions.

[0022] This disclosure (17) is a fluorination method according to this disclosure (15) or (16), wherein the fluorinating agent is solid at 25°C.

[0023] The present disclosure (18) is the fluorination method according to the present disclosure (16) or (17) in which the fluorine-containing compound is solid at 25°C.

[0024] The present disclosure (19) is a fluorination method of any combination of the present disclosures (16) to (18) in which the fluorine-containing compound is a fluorine-containing polymer.

[0025] The present disclosure (20) is a fluorination method of any combination of the present disclosures (16) to (19) in which the fluorine-containing compound is a fluorine-containing polymer containing a polymerization unit based on at least one monomer selected from the group consisting of tetrafluoroethylene, difluoroethylene, chlorotrifluoroethylene, hexafluoropropylene, perfluoro(alkyl vinyl ether), trifluoroethylene, and monofluoroethylene.

[0026] The present disclosure (21) is a fluorination method of any combination of the present disclosures (16) to (20) in which the fluorine-containing compound is at least one selected from the group consisting of polytetrafluoroethylene, polyvinylidene fluoride, and polychlorotrifluoroethylene.

[0027] The present disclosure (22) is a fluorination method of any combination of the present disclosures (16) to (21) in which the counter ion of the fluoride ion contains at least one selected from the group consisting of an alkali metal, an alkaline earth metal, and NR 1 4 (R 1 may be the same or different and is H or an organic group having 1 to 10 carbon atoms).

[0028] The present disclosure (23) is a fluorination method of any combination of the present disclosures (15) to (22) in which the fluorinating agent further contains a base.

[0029] The present disclosure (24) is the fluorination method according to the present disclosure (23) in which the base is solid at 25°C.

[0030] The present disclosure (25) is that the base is R 10OM (in the formula, R 10 H is an organic group with 1 to 10 carbon atoms, M is a metal or NR 1 4(R 1 The fluorination method according to disclosure (23) or (24) is at least one selected from the group consisting of compounds represented by ) and metal carbonates, which may be the same or different, and represent H or an organic group having 1 to 10 carbon atoms.

[0031] The present disclosure (26) is a fluorination method in any combination of any of the present disclosures (23) to (25), wherein the base is at least one selected from the group consisting of sodium hydroxide, potassium hydroxide, cesium hydroxide, cesium carbonate, sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide, sodium t-butoxide, and potassium t-butoxide.

[0032] The present disclosure (27) is a fluorination method in any combination of the present disclosure (23) to (26), wherein the content of the base relative to the fluorinating agent is 0.1 to 70% by mass.

[0033] The present disclosure (28) is a fluorination method in any combination with any of the present disclosures (16) to (27), wherein the fluorinating agent is obtained by mechanochemical treatment of a fluorine-containing compound and a base.

[0034] The present disclosure (29) is a fluorination method in any combination with any of the present disclosures (15) to (28), further comprising the step of purifying the crude product obtained by fluorination to recover the fluorinated target.

[0035] The present disclosure (30) is a fluorination method in any combination with any of the present disclosures (15) to (29) which carry out the fluorination in a dry manner.

[0036] The present disclosure (31) is a fluorination method in any combination of the present disclosures (15) to (30) wherein the fluorination is performed by mechanochemical treatment of the fluorinating agent and the object to be fluorinated.

[0037] The present disclosure (32) is a fluorination method in which the steps of obtaining the fluorinating agent and the fluorination step are carried out in succession, in any combination of any of the present disclosures (15) to (31).

[0038] This disclosure (33) is a fluorination method in any combination with any of this disclosure (15) to (32), wherein the amount of fluorinating agent used is 1.0 to 3.0 equivalents per equivalent of a group that can be substituted with a fluorine atom in the object.

[0039] This disclosure (34) is a fluorination method in any combination with any of the disclosures (15) to (33), wherein the target is an organic compound having at least one selected from the group consisting of chlorine atoms and bromine atoms. [Effects of the Invention]

[0040] This disclosure provides a fluorinating agent that can be manufactured by a simple method, and a fluorinating method using the fluorinating agent that can be manufactured by a simple method. [Modes for carrying out the invention]

[0041] The following provides a detailed explanation of this disclosure.

[0042] This disclosure relates to fluorinating agents containing fluorine-containing compounds and fluoride ions (hereinafter also referred to as fluorinating agent (1) of this disclosure). Since the fluorinating agent (1) of this disclosure has the above-described structure, it can be manufactured by a simple method. Furthermore, because a fluorine-containing compound with low hygroscopicity is present around the component containing fluoride ions, adhesion of the component is suppressed even when moisture is absorbed, and the powder state can be maintained. Therefore, the fluorinating agent (1) of this disclosure has excellent handling properties even when left in the atmosphere.

[0043] The fluorine-containing compound in the fluorinating agent (1) of this disclosure may be any compound having a fluorine atom, but may be any compound having a fluorine atom bonded to a carbon atom, and preferably is an organic compound having a fluorine atom bonded to a carbon atom. Furthermore, the above-mentioned fluorine-containing compound is preferably solid at 25°C, as this offers superior handling advantages.

[0044] The above-mentioned fluorine-containing compound is preferably a fluorine-containing polymer compound, and more preferably a fluorine-containing polymer.

[0045] The above-mentioned fluorine-containing polymer preferably contains polymerization units based on at least one monomer selected from the group consisting of tetrafluoroethylene [TFE], difluoroethylene, chlorotrifluoroethylene [CTFE], hexafluoropropylene [HFP], perfluoro(alkyl vinyl ether) [PAVE], trifluoroethylene, and monofluoroethylene. Examples of the above-mentioned difluoroethylenes include vinylidene fluoride [VdF] and 1,2-difluoroethylene. The above fluorine-containing polymer more preferably contains polymerization units based on at least one monomer selected from the group consisting of TFE, difluoroethylene, and CTFE; even more preferably contains polymerization units based on at least one monomer selected from the group consisting of TFE, VdF, and CTFE; even more preferably contains polymerization units based on at least one monomer selected from the group consisting of TFE and VdF; and particularly preferably contains polymerization units based on VdF.

[0046] The above-mentioned fluorine-containing polymer may be a fluororesin or a fluororubber.

[0047] The above fluororesins include polytetrafluoroethylene [PTFE], tetrafluoroethylene [TFE] / perfluoro(alkyl vinyl ether) [PAVE] copolymer [PFA], TFE / hexafluoropropylene [HFP] copolymer [FEP], ethylene [Et] / TFE copolymer [ETFE], Et / TFE / HFP copolymer [EFEP], polychlorotrifluoroethylene [PCTFE], chlorotrifluoroethylene [CTFE] / TFE copolymer, CTFE / TFE / PAVE copolymer, Examples include Et / CTFE copolymer, polyvinyl fluoride [PVF], polyvinylidene fluoride [PVdF], vinylidene fluoride [VdF] / TFE copolymer, VdF / HFP copolymer, VdF / TFE / HFP copolymer, VdF / HFP / (meth)acrylic acid copolymer, VdF / CTFE copolymer, VdF / pentafluoropropylene copolymer, VdF / PAVE / TFE copolymer, TFE / perfluoroalkyl allyl ether copolymer, etc., which can be used individually or in combination. The above perfluoroalkyl allyl ether is CF2=CFCF2-O-Rf 1 (Rf 1 It is a monomer represented by a perfluoroalkyl group having 1 to 5 carbon atoms.

[0048] Examples of the above-mentioned fluororubbers include vinylidene fluoride [VdF]-based fluororubbers, tetrafluoroethylene [TFE] / propylene [Pr]-based fluororubbers, TFE / Pr / VdF-based fluororubbers, ethylene [Et] / hexafluoropropylene [HFP]-based fluororubbers, Et / HFP / VdF-based fluororubbers, Et / HFP / TFE-based fluororubbers, fluorosilicone-based fluororubbers, and fluorophosphazene-based fluororubbers, which can be used individually or in combination.

[0049] Examples of the above-mentioned VdF-based fluororubbers include VdF / HFP copolymer, VdF / TFE / HFP copolymer, VdF / chlorotrifluoroethylene [CTFE] copolymer, VdF / CTFE / TFE copolymer, VdF / perfluoro(alkyl vinyl ether) [PAVE] copolymer, VdF / TFE / PAVE copolymer, VdF / HFP / PAVE copolymer, VdF / HFP / TFE / PAVE copolymer, VdF / TFE / Pr copolymer, VdF / Et / HFP copolymer, and VdF / polymer of a fluorine-containing monomer represented by the following formula (1). Formula (1): CH2=CFRf 2 (1) (In the formula, Rf 2 (These are linear or branched fluoroalkyl groups having 1 to 12 carbon atoms.)

[0050] The fluorine-containing polymer is preferably at least one selected from the group consisting of fluororesins and fluororubbers, more preferably at least one selected from the group consisting of PTFE, FEP, PFA, PVdF, PCTFE and fluororubbers, even more preferably at least one selected from the group consisting of PTFE, PVdF and PCTFE, even more preferably at least one selected from the group consisting of PTFE and PVdF, and PVdF is particularly preferred. Furthermore, as the fluorine-containing polymer, perhalose resins are also preferred, at least one selected from the group consisting of perfluororesins and PCTFE is more preferred, at least one selected from the group consisting of PTFE, PFA, FEP and PCTFE is even more preferred, and at least one selected from the group consisting of PTFE, PFA and FEP is even more preferred. Furthermore, as the fluorine-containing polymer, at least one selected from the group consisting of perfluororesins and polydifluoroethylenes is also preferred, and at least one selected from the group consisting of PTFE and polydifluoroethylenes is more preferred.

[0051] The above fluorine-containing compound does not have to be a polymer, as long as it is solid at 25°C; it may also be a fluorine-containing low-molecular-weight compound. The above fluorine-containing low-molecular-weight compound is given by the following general formula (I): Y-(CF2) x1 -(CH2) y1 -A (I) (In the formula, Y represents H or F. x1 represents an integer greater than or equal to 4, and y1 represents an integer between 0 and 3. A is -SO3M) I or -COOM I This indicates M I Compound (I) represented by the following general formula (II): where represents H, NH4, Li, Na, Mg, Al, K, or Ca. F-(CF2) X2 O(CFXCF2O) y2 -CFX-A (II) (In the formula, x² represents an integer greater than or equal to 1, and y² represents an integer between 0 and 10. X represents F or CF3. A represents -SO3M) II or -COOM II This indicates M II (1) represents H, NH4, Li, Na, Mg, Al, K, or Ca. The compound may be at least one fluorine-containing organic acid compound selected from the group consisting of compounds (II) represented by (1).

[0052] Examples of the above compound (I) include fluorocarboxylic acids and their salts, preferably perfluorocarboxylic acids and their salts, such as perfluorooctanoic acid and its salts (collectively referred to as "PFOA"). Examples of salts include ammonium salts and sodium salts, but ammonium salts are preferred, such as ammonium perfluorooctanoic acid (also known as "APFO"). Furthermore, compound (I) may also include fluorosulfonic acid and its salts, preferably perfluorosulfonic acid and its salts, such as perfluorooctanesulfonic acid and its salts (collectively referred to as "PFOS"). Examples of salts include ammonium salts and sodium salts. Examples of the above compound (II) include perfluoroether carboxylic acids and their salts, such as 2,3,3,3-tetrafluoro-2-[1,1,2,3,3,3-hexafluoro-2-(trifluoromethoxy)propoxy]-propanoic acid.

[0053] The above-mentioned fluorine-containing low-molecular-weight compound may be adsorbed onto an adsorbent. In this embodiment, the fluorinating agent (1) of the present disclosure may include a solid obtained by adsorbing the above-mentioned fluorine-containing low-molecular-weight compound onto an adsorbent. The above-mentioned adsorbent is not limited to any solid capable of adsorbing the above-mentioned fluorine-containing low-molecular-weight compound, but it is preferably at least one selected from the group consisting of activated carbon, silica gel, clay, metal-organic framework (MOF), and zeolite.

[0054] The above-mentioned fluorine-containing polymer may have been heated above its melting point, or it may have been molded. It may also have been pulverized after molding. From the viewpoint of reactivity in the manufacturing method described later, a smaller particle size is preferable.

[0055] The content of the above-mentioned fluorine-containing compound in the fluorinating agent (1) of this disclosure is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, even more preferably 0.5% by mass or more, and also preferably 90% by mass or less, more preferably 85% by mass or less, even more preferably 80% by mass or less, even more preferably 50% by mass or less, even more preferably 30% by mass or less, even more preferably 10% by mass or less, even more preferably 5% by mass or less, even more preferably 3% by mass or less, and particularly preferably 1% by mass or less. A lower content of the above-mentioned fluorine-containing compound is preferable.

[0056] The fluorinating agent (1) of this disclosure preferably contains substantially no fluorine-containing organic compounds. "Substantially free of fluorine-containing organic compounds" means that the organic fluorine content in the fluorinating agent (1) of this disclosure is 10% by mass or less, preferably 5% by mass or less, more preferably 3% by mass or less, even more preferably 2% by mass or less, even more preferably 1% by mass or less, and particularly preferably 0.1% by mass or less. The lower limit is not particularly limited and may be 0% by mass or 0.0001% by mass. The organic fluorine content in the fluorinating agent is measured by combustion ion chromatography. Organic fluorine refers to fluorine that is bonded to carbon.

[0057] The fluorinating agent (1) of this disclosure contains fluoride ions. The content of fluoride ions in the above fluorinating agent is preferably 0.5% by mass or more, more preferably 1.0% by mass or more, even more preferably 3.0% by mass or more, particularly preferably 5.0% by mass or more, also preferably 50% by mass or less, more preferably 30% by mass or less, even more preferably 20% by mass or less, particularly preferably 15% by mass or less, and may also be 10% by mass or less.

[0058] The fluorinating agent (1) of this disclosure typically contains a counterion along with a fluoride ion. The counterion is a metal, and NR 1 4(R 1 These may be the same or different, and preferably contain at least one selected from the group consisting of H or an organic group having 1 to 10 carbon atoms. These may be contained as cations. Examples of the above metals include 1- and 2-valent metals, specifically alkali metals (Group 1) or alkaline earth metals (Group 2), such as Na, K, Li, Cs, and Ca. Among these, alkali metals are preferred, Na, K, and Cs are more preferred, and K is even more preferred. NR 1 4 is ammonium (unsubstituted or substituted ammonium), and the four R's in the formula 1They may be the same or different. R 1 Preferably, the group is H or an organic group having 1 to 10 carbon atoms, and more preferably, H or an organic group having 1 to 4 carbon atoms.

[0059] The above counterions are alkali metals, alkaline earth metals, and NR 1 4(R 1 These may be the same or different, and it is more preferable to include at least one selected from the group consisting of H or an organic group having 1 to 10 carbon atoms, even more preferably to include at least one selected from the group consisting of alkali metals and alkaline earth metals, even more preferably to include an alkali metal, even more preferably to include at least one selected from the group consisting of Na, K and Cs, and particularly preferably to include K.

[0060] The amount of the above-mentioned counterions is preferably such that their charge balances with that of the above-mentioned fluoride ions.

[0061] The fluorinating agent (1) of this disclosure may contain a compound having a fluoride ion, or it may contain a compound having a fluoride ion and a counterion. Examples of such compounds include metal fluorides and ammonium fluoride, with metal fluorides being preferred, alkali metal fluorides being more preferred, and potassium fluoride being even more preferred.

[0062] The fluorinating agent (1) of this disclosure preferably further contains a base. A fluorinating agent containing a base together with a fluorine-containing compound can be produced by mechanochemical treatment of the fluorine-containing compound and the base, and therefore can be produced by a simpler method.

[0063] The above-mentioned base is a basic compound, and preferably a strongly basic compound. The above-mentioned base is preferably solid at 25°C for ease of handling.

[0064] The above base is preferably one whose pKa (acid dissociation constant at 25°C in water) is 40 or less, more preferably 35 or less, even more preferably 20 or less, and also preferably 8 or more, more preferably 9 or more, even more preferably 12 or more, and even more preferably 15 or more, in that respect the base can be manufactured using general-purpose equipment. pKa is measured by neutralization titration.

[0065] The above-mentioned base may be an inorganic base or an organic base, but an organic base is preferred because it allows the fluorinating agent to be manufactured using general-purpose equipment.

[0066] The above bases are metals and NR 1 4(R 1 These may be the same or different, and preferably contain at least one selected from the group consisting of H or an organic group having 1 to 10 carbon atoms. These may be contained as cations. The above metals and NR 1 The fourth point is the one mentioned above. The above bases are alkali metals, alkaline earth metals, and NR 1 4(R 1 These may be the same or different, and it is more preferable to include at least one selected from the group consisting of H or an organic group having 1 to 10 carbon atoms, even more preferably to include at least one selected from the group consisting of alkali metals and alkaline earth metals, even more preferably to include an alkali metal, even more preferably to include at least one selected from the group consisting of Na and K, and particularly preferably to include K.

[0067] The above base is R 10 OM (in the formula, R 10 H is an organic group with 1 to 10 carbon atoms, M is a metal or NR 1 4(R 1 (These may be the same or different, and represent H or an organic group having 1 to 10 carbon atoms). Examples include compounds represented by ), metal carbonates, metal acetates, cyclic amines, polyamines, etc. R 10 The number of carbon atoms in the organic group is preferably 2 or more, more preferably 3 or more, preferably 8 or less, and more preferably 6 or less. 10 Preferably, the group is H, or an alkyl group having a number of carbon atoms within the above range; more preferably, an alkyl group having a number of carbon atoms within the above range; and even more preferably, a methyl group, an ethyl group, or a t-butyl group. M metal and NR 1 4 includes the above-mentioned items. For M, metals are preferred, alkali metals or alkaline earth metals are more preferred, alkali metals are even more preferred, Na and K are even more preferred, and K is particularly preferred. As the metal of the above-mentioned metal carbonate, alkali metals or alkaline earth metals are preferred, alkali metals are more preferred, Na, K, and Cs are even more preferred, and Cs is particularly preferred. The metal of the above metal acetate is preferably an alkali metal or an alkaline earth metal, more preferably an alkali metal, even more preferably Na or K, and particularly preferably K. Examples of the above-mentioned cyclic amines include 1,8-diazabicyclo[5.4.0]-7-undecene (DBU) and its derivatives. Examples of the polyamines mentioned above include polyethyleneimine.

[0068] As for the above base, R is used because it allows for the production of fluorinating agents in a simpler manner. 10 At least one selected from the group consisting of compounds represented by OM and metal carbonates is preferred, as this makes the production of fluorinating agents in general-purpose equipment even easier. 10 In OM, R 10Compounds in which the group has 1 to 10 carbon atoms are preferred, metal alkoxides are more preferred, alkali metal alkoxides are even more preferred, at least one selected from the group consisting of alkali metal methoxides, alkali metal ethoxides and alkali metal t-butoxides is even more preferred, and at least one selected from the group consisting of sodium methoxides, potassium methoxides, sodium ethoxides, potassium ethoxides, sodium t-butoxides and potassium t-butoxides is particularly preferred. As the above base, at least one selected from the group consisting of alkali metal hydroxides, alkali metal carbonates, and alkali metal alkoxides is preferred, and at least one selected from the group consisting of sodium hydroxide, potassium hydroxide, cesium hydroxide, cesium carbonate, sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide, sodium t-butoxide, and potassium t-butoxide is more preferred.

[0069] The content of the base in the fluorinating agent (1) of this disclosure is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, even more preferably 0.1% by mass or more, and also preferably 90% by mass or less, more preferably 80% by mass or less, even more preferably 70% by mass or less, even more preferably 50% by mass or less, even more preferably 30% by mass or less, even more preferably 20% by mass or less, and particularly preferably 10% by mass or less. When the amount of base is within the above range, it is preferable from the viewpoint of yield because it prevents the decomposition of the substrate when the fluorinating agent is used in the fluorination process.

[0070] The fluorinating agent (1) of this disclosure preferably includes a compound having a structure in which the above-mentioned fluorine-containing compound has been defluorinated. The compound may have a structure in which at least some of the fluorine atoms of the above-mentioned fluorine-containing compound have been defluorinated. If the fluorinating agent (1) of the present disclosure contains a base, then at least some of the fluorine atoms in the fluorine-containing compound have a structure derived from the base, for example, R 10 O-(R 10 The compound may be substituted with a group represented by (for example, a hydroxyl group or an alkoxy group, preferably an alkoxy group) as described above. Fluorinating agents containing compounds having the above structure can be produced by a simpler method: decomposition (defluorination) of fluorinated compounds. The presence of a compound having the above structure in a fluorinating agent can be confirmed by removing components other than the fluorine-containing compound from the fluorinating agent by washing or other means, followed by analysis using XPS, FT-IR, solid-state NMR, etc., and by measuring the carbon and fluorine content before and after the reaction by elemental analysis.

[0071] The fluorinating agent (1) of this disclosure may contain other components as long as they do not impair its effect. Examples of these other components include general fillers, polymers, and the adsorbents mentioned above.

[0072] Examples of common fillers mentioned above include inorganic fillers such as glass fibers, glass beads, carbon fibers, spherical carbon, carbon black, graphite, silica, alumina, mica, silicon carbide, boron nitride, aluminum nitride, titanium oxide, bismuth oxide, cobalt oxide, magnesium oxide, molybdenum disulfide, bronze, gold, silver, copper, nickel, aluminum fluoride, carbon fluoride, and carbon black.

[0073] The above-mentioned common polymers include polyolefin resins such as polyethylene and polypropylene; polyamide [PA] resins such as nylon 6, nylon 11, nylon 12, nylon 46, nylon 66, nylon 610, nylon 612, and nylon MXD6; polyesters such as polyethylene terephthalate [PET], polybutylene terephthalate [PBT], polyarylate, aromatic polyesters (including liquid crystal polyesters), and polycarbonate [PC]; polyacetal [POM] resins; polyether resins such as polyphenylene oxide [PPO], modified polyphenylene ether, and polyetheretherketone [PEEK]; polyamideimide [PAI] resins such as polyaminobismaleimide; polysulfone resins such as polysulfone [PSF] and polyethersulfone [PES]; vinyl polymers such as ABS resin and poly-4-methylpentene-1 (TPX resin), as well as polyphenylene sulfide [PPS], polyketone sulfide, polyetherimide, polyimide [PI], and epoxy resins. The above nylon MXD6 is a crystalline polycondensate obtained from metaxylenediamine [MXD] and adipic acid. The general polymers mentioned above may be non-fluorinated polymers.

[0074] The content of the above-mentioned other components may be 50% by mass or less, preferably 30% by mass or less, more preferably 15% by mass or less, even more preferably 10% by mass or less, and may be 0% by mass or more, 0.01% by mass or more, 0.1% by mass or more, or 1% by mass or more.

[0075] The fluorinating agent (1) of this disclosure is preferably a solid at 25°C and also preferably a powder, in terms of its ease of handling.

[0076] The fluorinating agent (1) of this disclosure preferably has a maximum particle diameter of 7 mm or less, more preferably 6 mm or less, even more preferably 5 mm or less, particularly preferably 4 mm or less, and also preferably 10 μm or more, more preferably 100 μm or more, even more preferably 300 μm or more, and particularly preferably 500 μm or more. Fluorinating agents with a maximum particle diameter within the above range do not form clumps and are easy to handle.

[0077] The fluorinating agent (1) of this disclosure can be produced, for example, by mixing a fluorine-containing compound, a compound having fluoride ions, and a base as needed (hereinafter also referred to as production method (1)). The mixing method is not particularly limited, and known methods can be employed.

[0078] If the fluorinating agent (1) of this disclosure contains a base, it can also be produced by mechanochemical treatment of a fluorine-containing compound and a base (hereinafter also referred to as production method (2)). From the viewpoint of producing it in a simpler way, production method (2) is preferred. That is, it is preferable that the fluorinating agent (1) of this disclosure is obtained by mechanochemical treatment of a fluorine-containing compound and a base. Furthermore, it is also possible to obtain a fluorinating agent that is substantially free of fluorine-containing organic compounds by mechanochemical treatment. It is also preferable that the fluorinating agent (1) of this disclosure is obtained by mechanochemical treatment of a fluorine-containing compound and a base and is substantially free of fluorine-containing organic compounds. The manufacturing method (2) will be described in detail below.

[0079] The amount of the base used in the above mechanochemical treatment is preferably 0.01 equivalents or more, more preferably 0.05 equivalents or more, even more preferably 0.10 equivalents or more, and also preferably 10 equivalents or less, more preferably 8 equivalents or less, even more preferably 5 equivalents or less, even more preferably 3 equivalents or less, even more preferably 1 equivalent or less, and particularly preferably 0.8 equivalents or less, per 1 equivalent (molar equivalent) of the above fluorine-containing compound. In manufacturing method (2), mechanochemical treatment can be performed with a relatively small amount of base. When a small amount of base is used, there is an advantage in that the decomposition of the substrate can be prevented when the above-mentioned fluorinating agent is used in the fluorination step. If the above-mentioned fluorine-containing compound is a fluorine-containing polymer, the equivalent amount shall be calculated based on the monomers constituting the fluorine-containing polymer.

[0080] The above-described mechanochemical treatment is a treatment method that activates reactants (preferably solid reactants) by applying mechanical energy through methods such as shearing, compression, stretching, grinding, friction, kneading, mixing, dispersion, crushing, and shaking, thereby imparting structural changes, phase transitions, reactivity, adsorption properties, catalytic activity, etc. The method of mechanochemical treatment is not particularly limited, but examples include compression shear treatment, impact treatment, and mixed shear friction treatment, with the impact treatment method being preferred.

[0081] The apparatus for mechanochemical processing is not particularly limited as long as it can apply mechanical energy in the manner described above, and known pulverizers and mixers can be used. For example, pulverizers such as ball mills, rod mills, jet mills, vibratory mills, and SAG mills; grinders such as rotary stone mills and mortars; (horizontal axis rotation) container rotary mixing devices such as horizontal cylindrical, V-type, double cone, square cube, S-type and continuous V-type; (baffle plate) container rotary mixing devices such as horizontal cylindrical, V-type, double cone and ball mill types; (rotational vibration) container rotary mixing devices such as rocking type and cross rotary type; (horizontal axis) Examples include rotary fixed-container mixing devices; ribbon type, screw type, planetary type, turbine type, high-speed fluid type, rotating disc type and Mahler type (vertical axis rotation) fixed-container mixing devices; vibrating mill type and sieve type (vibration) fixed-container mixing devices; non-uniform fluidized bed, swirling fluidized bed, riser tube type and jet pump type (fluidization) fluid motion mixing devices; gravity type and static mixer (gravity) fluid motion mixing devices; twin-shaft kneaders, single-shaft kneaders, mixers, roll mills, etc.

[0082] As the apparatus for performing the above mechanochemical treatment, an apparatus using balls is preferred, and a ball mill is more preferred. A ball mill (excluding a planetary ball mill) is preferred because it can be manufactured using a more general-purpose apparatus. This configuration is particularly suitable when the base is an organic base.

[0083] The above mechanochemical treatment can be carried out using a planetary mill, but it is preferable not to use a planetary mill. While a planetary mill is a device that can supply high energy, it is also a device that generates a large amount of wear particles originating from the device itself. For example, Fig. 3 in J.Soc. Powder Technol., Japan, 44, 186-190 (2007) [https: / / www.jstage.jst.go.jp / article / sptj1978 / 44 / 3 / 44_3_186 / _pdf / -char / ja] describes the relationship between the rotational speed of a planetary mill and the amount of wear particles generated from the device, showing that a certain amount of wear particles are generated by a planetary mill. When the composition after the reaction is used as a fluorinating agent, it is preferable that it does not contain impurities. By performing the mechanochemical treatment under conditions that minimize the generation of wear particles originating from the device, without using a planetary mill, a composition suitable for use as a fluorinating agent can be obtained. In addition, methods using general-purpose devices such as ball mills instead of planetary mills have the advantage of being easy to industrialize. In particular, if the above base is an organic base, it is preferable not to use a planetary mill.

[0084] The temperature for the above mechanochemical treatment is preferably 5°C or higher, more preferably 10°C or higher, even more preferably 15°C or higher, even more preferably 20°C or higher, and also preferably 300°C or lower, more preferably 250°C or lower, even more preferably 200°C or lower, and even more preferably 160°C or lower.

[0085] When the above mechanochemical treatment is performed using a ball mill (excluding planetary ball mills), the shaking conditions can be determined according to the equipment and balls used. For example, when processing a jar of about 1 to 20 mL using one stainless steel ball with a diameter of about 1 to 15 mm, the shaking can be performed at a preferred speed of 100 rpm or more, more preferably 300 rpm or more, even more preferably 500 rpm or more, and also preferably 1800 rpm or less, more preferably 1600 rpm or less, and even more preferably 1500 rpm or less.

[0086] When the above mechanochemical treatment is performed using a ball mill (excluding a planetary ball mill), the duration of the mechanochemical treatment is preferably 5 minutes or more, more preferably 10 minutes or more, even more preferably 20 minutes or more, and also preferably 500 minutes or less, more preferably 300 minutes or less, even more preferably 200 minutes or less, and even more preferably 100 minutes or less.

[0087] The above mechanochemical treatment can be carried out in any atmosphere, such as in air, inert gas, or in a vacuum. From the viewpoint of low cost, it is preferable to carry it out in air.

[0088] The above mechanochemical treatment can be carried out in the absence of a solvent, but may also be carried out in the presence of a small amount of solvent if necessary. The presence of a small amount of solvent may promote the mixing of the components. The amount of solvent used is preferably 0.001 μl / mg or more, more preferably 0.01 μl / mg or more, more preferably 0.05 μl / mg or more, and more preferably 3.0 μl / mg or less, more preferably 1.0 μl / mg or less, and even more preferably 0.5 μl / mg or less, based on the total mass of the fluorine-containing compound and the base.

[0089] As solvents for the above mechanochemical treatment, organic solvents such as ethers, nitriles, esters, aromatics, hydrocarbons, alcohols, and halogens are preferred. Examples of the above organic solvents include esters such as methyl acetate, ethyl acetate, propyl acetate, n-butyl acetate, and tert-butyl acetate; ketones such as acetone, methyl ethyl ketone, and cyclohexanone; aliphatic hydrocarbons such as hexane, cyclohexane, octane, nonane, decane, undecane, dodecane, and mineral spirits; aromatic hydrocarbons such as benzene, toluene, xylene, naphthalene, and solvent naphtha; alcohols such as methanol, ethanol, tert-butanol, iso-propanol, and ethylene glycol monoalkyl ethers; cyclic ethers such as tetrahydrofuran, tetrahydropyran, and dioxane; nitriles such as acetonitrile and propionitrile; amides such as dimethyl sulfoxide, N,N-dimethylformamide, and N,N-dimethylacetamide; halogenated hydrocarbons such as dichloromethane, dichloroethane, and chloroform, or mixtures thereof. Among the above solvents, cyclic ethers are preferred.

[0090] The above mechanochemical treatment may also be carried out in a dry manner. Carrying it out in a dry manner means that the amount of liquid in the reaction system is 5% by mass or less, preferably 1% by mass or less, more preferably 0.1% by mass or less, and even more preferably 0.01% by mass or less.

[0091] The above mechanochemical treatment allows the fluorine-containing compound to be reacted. The reaction may be one that generates fluoride ions, and is preferably a defluorination reaction.

[0092] The above mechanochemical treatment yields a composition containing a fluorine-containing compound, a base, and fluoride ions (and counterions), and this composition can be used as is as the fluorinating agent (1) of the present disclosure.

[0093] This disclosure also relates to a fluorinating agent (hereinafter also referred to as fluorinating agent (2) of this disclosure), which is a composition obtained by mechanochemical treatment of a fluorine-containing compound and a base. The fluorinating agent (2) of this disclosure has excellent properties as a fluorinating agent because it is obtained by a specific treatment.

[0094] Examples of fluorine-containing compounds and bases in the fluorinating agent (2) of this disclosure are the same as those described in the fluorine-containing compounds and bases in the fluorinating agent (1) of this disclosure, and the preferred forms are also the same.

[0095] The mechanochemical treatment in the fluorinating agent (2) of this disclosure includes the same treatment as the manufacturing method (2) described in the fluorinating agent (1) of this disclosure, and the preferred form is also the same.

[0096] The fluorinating agent (2) of this disclosure preferably contains substantially no fluorine-containing organic compounds. "Substantially free of fluorine-containing organic compounds" means that the organic fluorine content in the fluorinating agent (2) of this disclosure is 10% by mass or less, preferably 5% by mass or less, more preferably 3% by mass or less, even more preferably 2% by mass or less, even more preferably 1% by mass or less, and particularly preferably 0.1% by mass or less. The lower limit is not particularly limited and may be 0% by mass or 0.0001% by mass. The content of organofluorine in the composition is measured by combustion ion chromatography. Organic fluorine refers to fluorine that is bonded to carbon.

[0097] The fluorinating agents (1) and (2) of this disclosure can be used in the production of various compounds having fluorine atoms, and are particularly suitable for use in the production of fluorine-containing organic compounds. Furthermore, the fluorinating agents (1) and (2) of this disclosure can be suitably used as fluorinating agents in the fluorination method of this disclosure described later.

[0098] This disclosure also relates to a fluorination method (hereinafter also referred to as fluorination method (1) of this disclosure) which includes a step of fluorinating an object using a fluorinating agent containing a fluorine-containing compound and fluoride ions. Since the fluorination method (1) of this disclosure has the above configuration, fluorination can be performed using a fluorinating agent that can be manufactured by a simple method. Furthermore, because a fluorine-containing compound with low hygroscopicity is present around the component having fluoride ions, adhesion of the component is suppressed even when moisture is absorbed, and the fluorinating agent can maintain its powder state, so fluorination can be performed using a fluorinating agent that is easy to handle even when left in the atmosphere.

[0099] This disclosure also relates to a fluorination method (hereinafter also referred to as the fluorination method (2) of this disclosure) which includes a step of fluorinating an object using the fluorinating agent (2) of this disclosure. The fluorination method (2) of this disclosure can achieve a good fluorination reaction by using a fluorinating agent obtained by a specific treatment.

[0100] In this specification, the fluorination methods (1) and (2) of this disclosure are collectively referred to as "the fluorination methods of this disclosure."

[0101] The fluorinating agent used in the fluorinating method (1) of this disclosure may be the same as the fluorinating agent (1) of this disclosure described above. The fluorinating agent used in the fluorinating method (2) of this disclosure is the fluorinating agent (2) of this disclosure described above.

[0102] The object to be fluorinated may have a group that can be substituted with a fluorine atom. Preferably, the object is a compound having at least one group that can react nucleophilically with a fluorine atom, and more preferably, an organic compound having at least one group that can react nucleophilically with a fluorine atom.

[0103] The above-mentioned groups that can react nucleophilically with fluorine atoms include chlorine atoms, bromine atoms, iodine atoms, hydrogen atoms, hydroxyl groups, and organic groups. The number of carbon atoms in the above organic group is preferably 1 or more, more preferably 2 or more, and preferably 10 or less, and more preferably 7 or less. The above organic groups include alkenyl groups, alkynyl groups, and OSO2R. 2 (R 2 Examples include organic groups with 1 to 10 carbon atoms, carboxyl groups, etc. The above-mentioned nucleophilically reactive group with a fluorine atom is preferably at least one selected from the group consisting of a chlorine atom, a bromine atom, an iodine atom, and a hydroxyl group; more preferably at least one selected from the group consisting of a chlorine atom, a bromine atom, and a hydroxyl group; even more preferably at least one selected from the group consisting of a chlorine atom and a bromine atom; and even more preferably a chlorine atom.

[0104] The above fluorination can be carried out by bringing the fluorinating agent into contact with the object. The method of contact is not limited, and any known method can be used.

[0105] In the above fluorination, the amount of fluorinating agent used is preferably 1.0 equivalent or more, more preferably 1.3 equivalents or more, even more preferably 2.0 equivalents or more, and preferably 10 equivalents or less, more preferably 5.0 equivalents or less, and even more preferably 3.0 equivalents or less, per equivalent of 1 equivalent of a group that can be substituted for a fluorine atom in the target object. In calculating the equivalent amount of the fluorinating agent described above, the molecular weight of the fluorinating agent is determined by the following formula, where M1 is the molecular weight of the fluorine-containing compound (or its constituent monomer in the case of a polymer), M2 is the molecular weight of the base, and x:1 is the equivalent ratio of the two in the fluorinating agent (fluorine-containing compound:base). Molecular weight of fluorinating agent = xM1 + M2

[0106] The above fluorination is preferably carried out in the presence of a solvent. Examples of the solvent include water, organic solvents, or mixtures thereof. Examples of the above organic solvents include esters such as methyl acetate, ethyl acetate, propyl acetate, n-butyl acetate, and tert-butyl acetate; ketones such as acetone, methyl ethyl ketone, and cyclohexanone; aliphatic hydrocarbons such as hexane, cyclohexane, octane, nonane, decane, undecane, dodecane, and mineral spirits; aromatic hydrocarbons such as benzene, toluene, xylene, naphthalene, and solvent naphtha; alcohols such as methanol, ethanol, tert-butanol, iso-propanol, and ethylene glycol monoalkyl ethers; cyclic ethers such as tetrahydrofuran, tetrahydropyran, and dioxane; nitriles such as acetonitrile and propionitrile; amides such as dimethyl sulfoxide, N,N-dimethylformamide, and N,N-dimethylacetamide; halogenated hydrocarbons such as dichloromethane, dichloroethane, and chloroform, or mixtures thereof.

[0107] The temperature for the fluorination described above is preferably 5°C or higher, more preferably 10°C or higher, even more preferably 15°C or higher, even more preferably 20°C or higher, and also preferably 200°C or lower, more preferably 150°C or lower, even more preferably 100°C or lower, and even more preferably 50°C or lower.

[0108] The fluorination time is preferably 5 minutes or more, more preferably 10 minutes or more, even more preferably 20 minutes or more, and also preferably 50 hours or less, more preferably 30 hours or less, even more preferably 20 hours or less, and even more preferably 15 hours or less.

[0109] It is also preferable to carry out the above fluorination in a dry manner. It has been found that the fluorination reaction proceeds even in a dry manner when the above fluorinating agent is used. Carrying out fluorination in a dry manner means that the amount of liquid in the fluorination reaction system is 5% by mass or less, preferably 1% by mass or less, more preferably 0.1% by mass or less, and even more preferably 0.01% by mass or less.

[0110] It is also preferable to carry out the above fluorination by mechanochemical treatment of the fluorinating agent and the target object. When the above fluorination is carried out by dry method, it is particularly preferable to employ mechanochemical treatment. The conditions for the mechanochemical treatment of the above-mentioned fluorinating agent with the above-mentioned object can be the same as those described in the method for producing the fluorinating agent of this disclosure (2).

[0111] It is also preferable to carry out the step of obtaining the fluorinating agent and the step of fluorinating the product in succession. In this embodiment, it is preferable to carry out both steps in the same reaction vessel, and it is also preferable to carry out the fluorinating step after the step of obtaining the fluorinating agent without isolating or purifying the product. Furthermore, it is preferable to carry out the fluorinating step by mechanochemical treatment. While the specific implementation method is not limited, it is preferable, for example, that after the completion of the step to obtain the fluorinating agent, the substance to be fluorinated is added to the same reaction vessel without removing the contents of the reaction vessel, and the fluorination reaction is carried out.

[0112] The above fluorination process yields a crude product containing the fluorinated target (a compound in which a group that can be substituted with a fluorine atom is replaced with a fluorine atom).

[0113] The fluorination method of this disclosure may also preferably include a step of purifying the crude product obtained by fluorination to recover the fluorinated target. The purification method is not particularly limited, and known methods can be used.

[0114] The fluorination method of this disclosure can be used to produce various compounds having fluorine atoms, and is particularly suitable for the production of fluorine-containing organic compounds.

[0115] Although embodiments have been described above, it should be understood that various modifications to the form and details are possible without departing from the spirit and scope of the claims. [Examples]

[0116] The present disclosure will now be further described with reference to examples, but the present disclosure is not limited to these examples.

[0117] <Fluoride ions after the reaction (F - ) and measurement of base content > It was measured by ion chromatography. After the reaction, the liquid was removed by filtration with distilled water, and the residue was diluted with distilled water. Measurements were then performed using a Tosoh IC-8100ST equipped with a column (TSKgel® SuperIC-Anion HS) under conditions of oven temperature 40°C and flow rate 1.50 mL / min.

[0118] The following materials (all solid at 25°C) were used in the examples and reference examples. Fluororesin A-1: ​​PVdF (VdF homopolymer, manufactured by BLD Pharmatech Ltd.), powder Fluororesin A-2: PTFE (TFE homopolymer, manufactured by Kitamura Co., Ltd., KTL-2N) Fluororesin A-3: PCTFE (CTFE homopolymer, manufactured by Sigma-Aldrich), powder Base B-1: tBuOK (organic base, pKa=17) Base B-2: KOMe (organic base, pKa=16) Base B-3: KOEt (organic base, pKa=17) Base B-4: tBuONa (organic base, pKa=17) Base B-5: CsOH·H2O (inorganic base, pKa=15) Base B-6: Cs2CO3 (inorganic base, pKa=10) Base B-7: KOH (inorganic base, pKa=14.7) Base B-8: NaOH (inorganic base, pKa=13)

[0119] Example 1 A 10 mL stainless steel jar was filled with a stainless steel ball (10 mm), 0.5 eq. (equivalent) of fluoropolymer A-1 (128 mg, 2.0 mmol, calculated based on the molecular weight of the constituent monomer VdF (64.03)), 1.0 eq. of base B-1 (449 mg, 4.0 mmol), and anhydrous THF (0.5 μL / mg of fluoropolymer). The jar was closed and placed in a ball mill (Retsch Mixer Mill MM 400). Mechanochemical treatment with the ball mill was carried out at room temperature (25 °C) at 30 Hz for 60 minutes. After completion, the jar was opened, washed with water, and concentrated in a vacuum. The resulting composition (reaction mixture) was diluted with water and analyzed by ion chromatography. The resulting composition was a solid (powder) at 25°C and contained fluororesin A-1, <59% by mass of base B-1, and 1.8% by mass of fluoride ions. The counterion of the fluoride ion is K. The yield of KF is shown in Table 1. The yield was calculated with 100% being the case when all of the counterions K of base B-1 were converted to KF.

[0120] Example 2 A 10 mL stainless steel jar contained a stainless steel ball (10 mm), 5.0 eq. (equivalent) of fluoropolymer A-1 (1280 mg, 20 mmol, calculated based on the molecular weight of the constituent monomer VdF (64.03)), and 1.0 eq. of base B-1 (449 mg, 4.0 mmol). The jar was closed and placed in a ball mill (Retsch Mixer Mill MM 400). Mechanochemical treatment with the ball mill was carried out at room temperature (25 °C) at 30 Hz for 30 minutes. After completion, the jar was opened, washed with water, and concentrated in a vacuum. The resulting composition (reaction mixture) was diluted with water and analyzed by ion chromatography. The resulting composition was a solid (powder) at 25°C and contained fluororesin A-1, base B-1, and 2.9% by mass of fluoride ions. The counterion of the fluoride ion is K. The yield of KF is shown in Table 1.

[0121] Example 3 Mechanochemical treatment was performed in the same manner as in Example 1, except that the amount of fluororesin A-1 was changed to 3.0 eq. The resulting composition was a solid (powder) at 25°C and contained fluororesin A-1, <7.3% by mass of base B-1, and 7.7% by mass of fluoride ions. The counterion of the fluoride ion is K. The yield of KF is shown in Table 1.

[0122] Example 4 The mechanochemical treatment was carried out in the same manner as in Example 1, except that 0.5 eq. of fluororesin A-1 was replaced with 1.0 eq. of fluororesin A-2 (1200 mg, 12.0 mmol, calculated based on the molecular weight of the constituent monomer TFE (100.02)), and the outer surface of the reaction vessel was heated to 300°C with a heat gun (the internal temperature was estimated to be approximately 150°C). The resulting composition was a solid (powder) at 25°C and contained fluororesin A-2, base B-1, and 4.2% by mass of fluoride ions. The counterion of the fluoride ion is K. The yield of KF is shown in Table 1.

[0123] Example 5 Mechanochemical treatment was performed in the same manner as in Example 4, except that 1.0 eq. of fluororesin A-2 was replaced with 3.0 eq. of fluororesin A-3, the reaction time was changed to 180 minutes, and the external surface of the reaction vessel was heated to 200°C with a heat gun (the internal temperature was estimated to be approximately 100°C). The resulting composition was a solid (powder) at 25°C and contained fluororesin A-3, base B-1, and 2.0% by mass of fluoride ions. The counterion of the fluoride ion is K. The yield of KF is shown in Table 1.

[0124] Example 6 Mechanochemical treatment was performed in the same manner as in Example 1, except that the amount of fluororesin A-1 was changed to 2.0 eq. and the base to B-2 (1.0 eq.). The resulting composition was a solid (powder) at 25°C and contained fluororesin A-1, <1.7% by mass of base B-2, and 9.1% by mass of fluoride ions. The counterion of the fluoride ion is K. The yield of KF is shown in Table 1.

[0125] Example 7 Mechanochemical treatment was performed in the same manner as in Example 6, except that the base was changed to B-3. The resulting composition was a solid (powder) at 25°C and contained fluororesin A-1, base B-3, and 8.8% by mass of fluoride ions. The counterion of the fluoride ion is K. The yield of KF is shown in Table 1.

[0126] Example 8 Mechanochemical treatment was carried out in the same manner as in Example 6, except that the base was changed to B-4. The resulting composition was a solid (powder) at 25°C and contained fluororesin A-1, base B-4, and 8.1% by mass of fluoride ions. The counterion of the fluoride ion is Na. The yield of NaF is shown in Table 1.

[0127] Example 9 Mechanochemical treatment was carried out in the same manner as in Example 6, except that the base was changed to B-5. The resulting composition was a solid (powder) at 25°C and contained fluororesin A-1, base B-5, and 8.0% by mass of fluoride ions. The counterion of the fluoride ion is Cs. The yield of CsF is shown in Table 1.

[0128] Example 10 Mechanochemical treatment was carried out in the same manner as in Example 6, except that the base was changed to B-6. The resulting composition was a solid (powder) at 25°C and contained fluororesin A-1, base B-6, and 0.2% by mass of fluoride ions. The counterion of the fluoride ion is Cs. The yield of CsF is shown in Table 1.

[0129] Example 11 Mechanochemical treatment was performed in the same manner as in Example 1, except that the amount of fluororesin A-1 was changed to 3.0 eq. and base B-1 was changed to base B-7. The resulting composition was a solid (powder) at 25°C and contained fluororesin A-1, base B-7, and 5.2% by mass of fluoride ions. The counterion of the fluoride ion is K. The yield of KF is shown in Table 1.

[0130] Example 12 Mechanochemical treatment was performed in the same manner as in Example 1, except that the amount of fluororesin A-1 was changed to 3.0 eq. and base B-1 was changed to base B-8. The resulting composition was a solid (powder) at 25°C and contained fluororesin A-1, base B-8, and 1.9% by mass of fluoride ions. The counterion of the fluoride ion is Na. The yield of NaF is shown in Table 1.

[0131] [Table 1]

[0132] Example 13 A nitrogen gas was sealed into an oven-drying vial fitted with a magnetic stirring rod. Next, the composition obtained in Example 2 (172.94 mg, 0.4 mmol, 2.0 eq.), ethyl acetate (1 mL), and p-Toluoyl Chloride (26.43 μL, 0.2 mmol, 1.0 eq.) were added sequentially. The vial was stirred under a nitrogen gas atmosphere at room temperature (25°C) for 12 hours. The yield of the obtained p-Toluoyl Fluoride was measured using 4-fluoroanisole as an internal standard. 19 The measurement by 1F NMR showed a percentage of 52%.

[0133] Reference example 1 p-Toluoyl Fluoride was obtained in the same manner as in Example 4, except that 1.5 eq. of KF obtained by spray drying was used instead of the composition obtained in Example 2. The yield was 55%.

[0134] It has been found that using the fluorinating agent disclosed herein allows fluorination to proceed with an efficiency comparable to that of KF, a conventionally known fluorinating agent.

[0135] Reference example 2 The sample obtained in Example 3, which was preheated and dried at 120°C, and the KF produced by spray drying were left in the air for 5 hours, and their state after standing was observed. The KF produced by spray drying deliquesced and solidified, failing to maintain its powdery state and compromising its handling properties for use as KF. On the other hand, the sample obtained in Example 3 maintained its powdery state, retained its handling properties, and was ready for direct use as a fluorinating agent.

[0136] The fluorinating agent disclosed herein has been found to have superior atmospheric storage properties and superior handling properties compared to KF, a conventionally known fluorinating agent.

[0137] Example 14 In a glass reaction vessel equipped with a magnetic stirring rod, the composition obtained in Example 3 (0.3 mmol, 1.5 eq.), sulfonyl chloride (R-SO2Cl, 0.2 mmol, 1.0 eq.) shown in Table 2, distilled water (2.0 eq., 0.4 mmol), and acetone (0.2 M) as a solvent were added. After stirring the reaction mixture at room temperature for 30 minutes, the resulting suspension or crude product was filtered through a silica plug eluted with siRNA to remove insoluble by-products, and the solvent was removed by reducing the pressure to obtain the corresponding sulfonyl fluoride (R-SO2F). The yield of the obtained sulfonyl fluoride (Entries 9, 10 and 11 are shown below) 19 The yields calculated using 4-fluoroanisole as an internal standard via 1F NMR are shown in Table 2. (All other yields are isolation yields.)

[0138] [Table 2]

[0139] Example 15 Nitrogen gas was sealed into an oven-drying vial fitted with a magnetic stirring rod. Next, the composition obtained in Example 2 (0.2 mmol, 1.5 eq.), dried ethyl acetate (1 mL), and the acyl chloride (R-COCl, 0.2 mmol, 1.0 eq.) shown in Table 3 were added sequentially. The vial was stirred under a nitrogen gas atmosphere at room temperature (25°C) for 12 hours. Isolation and purification were performed using silica gel column chromatography to obtain the corresponding acyl fluoride (R-COF). The yield (isolation yield) of the obtained acyl fluoride is shown in Table 3.

[0140] [Table 3]

[0141] Example 16 The composition obtained in Example 3 (2.0 eq., 0.4 mmol), the bromide shown in Table 4 (R-Br, 0.2 mmol, 1.0 eq.), 18-crown-6-ether (1.0 eq.), H2O (18 μL, 5.0 eq.), and anhydrous tBuOH (0.8 mL) were added to a glass reaction vessel. After stirring at 100°C for the time shown in Table 4, the resulting suspension was cooled to room temperature, filtered with ELISA to remove insoluble by-products, and concentrated under reduced pressure to remove the solvent. Isolation and purification were performed using silica gel column chromatography to obtain the corresponding fluoride (RF). The yield (isolation yield) of the obtained fluoride is shown in Table 4.

[0142] [Table 4]

[0143] Example 17 A 1.5 mL stainless steel jar was filled with a stainless steel ball (5 mm), the composition obtained in Example 3 (1.5 eq., 0.3 mmol), and the sulfonyl chloride (R-SO2Cl, 0.2 mmol, 1.0 eq.) shown in Table 5. The jar was closed and placed in a ball mill (Retsch Mixer Mill MM 400). Mechanochemical treatment with the ball mill was performed at room temperature (25 °C) at 30 Hz for 5 minutes. After completion, the jar was opened, washed with ethyl acetate, and concentrated under vacuum to obtain the corresponding sulfonyl fluoride (R-SO2F). The yields of the obtained sulfonyl fluoride (Entry 1 yields measured by gas chromatography (GC) with mesitylene as an internal standard; all others are isolation yields) are shown in Table 5.

[0144] [Table 5]

[0145] Example 18 A 1.5 mL stainless steel jar contained a stainless steel ball (5 mm), 5.0 eq. of fluoropolymer A-1, and 1.1 eq. of base B-1. The jar was closed and placed in a ball mill (Retsch Mixer Mill MM 400). Mechanochemical treatment with the ball mill was carried out for 60 minutes at room temperature (25°C) and 30 Hz. After completion, the jar was opened and sulfonyl chloride (R-SO2Cl, 0.2 mmol, 1.0 eq.) shown in Table 6 was added to the mixture. The jar was closed and mechanochemical treatment with the ball mill was carried out for 5 minutes at room temperature (25°C) and 30 Hz. After completion, the jar was opened, washed with ethyl acetate, and concentrated under vacuum. The yield of the desired sulfonyl fluoride (R-SO2F) obtained was measured using hexafluorobenzene as an internal standard. 19 The results were measured by 1F NMR. The results are shown in Table 6.

[0146] [Table 6]

[0147] Example 19 The composition obtained in Example 3 (1.5 eq., 0.3 mmol), 1-bromooctane (1.0 eq., 0.2 mmol), water (18 μL, 5.0 eq.), and anhydrous tBuOH (0.8 mL) were added to a glass reaction vessel. Fluorination was carried out in the same manner as in Example 13, except that the mixture was stirred at 100°C for 10 hours. The yield of fluoride was 74%.

[0148] Example 20 Fluorination was carried out in the same manner as in Example 13, except that 0.5 eq. of fluororesin A-1, 1.0 eq. of base B-1, and sulfonyl chloride were replaced with p-toluenesulfonyl chloride. The fluorination yield was 1%.

[0149] Example 21 Fluorination was carried out in the same manner as in Example 20, except that the fluororesin A-1 was changed to 2.0 eq. The fluorination yield was 90%.

[0150] Example 22 The composition obtained in Example 11 (1.5 eq., 0.3 mmol), p-toluenesulfonyl chloride (1.0 eq., 0.2 mmol), and water (8 μL, 2.0 eq.) were added. Fluorination was carried out in the same manner as in Example 13, except that the mixture was stirred at 25°C for 30 minutes. The yield of fluoride was 58%.

[0151] Experimental Example 23 Commercially available KF (298 mg) was weighed in a glove box, and its mass (X mg) was measured after 24 hours of storage in the atmosphere. The mass increase rate was calculated using the following formula and was found to be 20%. Growth rate (%) = (X - 298) / 298 × 100 The mass increase rate of the composition obtained in Example 1 was similarly determined to be 12%.

Claims

1. A fluorinating agent containing fluorine-containing compounds and fluoride ions.

2. The fluorinating agent according to claim 1, which is solid at 25°C.

3. The counterions of the fluoride ions are alkali metals, alkaline earth metals, and NR １ ４ (R １ The fluorinating agent according to claim 1 or 2, wherein the two elements may be the same or different, and each element is selected from the group consisting of H or an organic group having 1 to 10 carbon atoms.

4. The fluorinating agent according to claim 1 or 2, further comprising a base.

5. The fluorinating agent according to claim 4, wherein the base is solid at 25°C.

6. The fluorinating agent according to claim 4, wherein the pKa of the base is 8 to 40.

7. The aforementioned base, R １０ OM (in the formula, R １０ H is an organic group having 1 to 10 carbon atoms, M is a metal or NR １ ４ (R １ The fluorinating agent according to claim 4, wherein (which may be the same or different, represents H or an organic group having 1 to 10 carbon atoms). The fluorinating agent is selected from the group consisting of compounds represented by () and metal carbonates.

8. The fluorinating agent according to claim 4, wherein the base is at least one selected from the group consisting of sodium hydroxide, potassium hydroxide, cesium hydroxide, cesium carbonate, sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide, sodium t-butoxide, and potassium t-butoxide.

9. The fluorinating agent according to claim 4, wherein the base content is 0.1 to 70% by mass.

10. The fluorinating agent according to claim 1 or 2, wherein the fluorine-containing compound is solid at 25°C.

11. The fluorinating agent according to claim 1 or 2, wherein the fluorine-containing compound is a fluorine-containing polymer.

12. The fluorinating agent according to claim 1 or 2, wherein the fluorine-containing compound is a fluorine-containing polymer comprising a polymerization unit based on at least one monomer selected from the group consisting of tetrafluoroethylene, difluoroethylene, chlorotrifluoroethylene, hexafluoropropylene, perfluoro(alkyl vinyl ether), trifluoroethylene, and monofluoroethylene.

13. The fluorinating agent according to claim 1 or 2, wherein the fluorine-containing compound is at least one selected from the group consisting of polytetrafluoroethylene, polyvinylidene fluoride, and polychlorotrifluoroethylene.

14. A fluorinating agent, which is a composition obtained by mechanochemical treatment of a fluorine-containing compound and a base.

15. A fluorination method comprising the step of fluorinating an object using the fluorinating agent described in claim 14.

16. A fluorination method comprising the step of fluorinating a target object using a fluorinating agent containing a fluorine-containing compound and fluoride ions.

17. The fluorination method according to claim 15 or 16, wherein the fluorinating agent is solid at 25°C.

18. The fluorination method according to claim 16, wherein the fluorine-containing compound is solid at 25°C.

19. The fluorination method according to claim 16, wherein the fluorine-containing compound is a fluorine-containing polymer.

20. The fluorination method according to claim 16, wherein the fluorine-containing compound is a fluorine-containing polymer comprising a polymerization unit based on at least one monomer selected from the group consisting of tetrafluoroethylene, difluoroethylene, chlorotrifluoroethylene, hexafluoropropylene, perfluoro(alkyl vinyl ether), trifluoroethylene, and monofluoroethylene.

21. The fluorination method according to claim 16, wherein the fluorine-containing compound is at least one selected from the group consisting of polytetrafluoroethylene, polyvinylidene fluoride, and polychlorotrifluoroethylene.

22. The counter ion of the fluoride ion is an alkali metal, an alkaline earth metal, and NR １ ４ (R １ may be the same or different and is at least one selected from the group consisting of H or an organic group having 1 to 10 carbon atoms). The fluorination method according to claim 16.

23. The fluorination method according to claim 15 or 16, wherein the fluorinating agent further comprises a base.

24. The fluorination method according to claim 23, wherein the base is solid at 25°C.

25. The aforementioned base, R １０ OM (in the formula, R １０ H is an organic group having 1 to 10 carbon atoms, M is a metal or NR １ ４ (R １ The fluorination method according to claim 23, wherein (which may be the same or different, represents H or an organic group having 1 to 10 carbon atoms). The fluorination method according to claim 23, wherein at least one is selected from the group consisting of compounds represented by () and metal carbonates.

26. The fluorination method according to claim 23, wherein the base is at least one selected from the group consisting of sodium hydroxide, potassium hydroxide, cesium hydroxide, cesium carbonate, sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide, sodium t-butoxide, and potassium t-butoxide.

27. The fluorination method according to claim 23, wherein the content of the base relative to the fluorinating agent is 0.1 to 70% by mass.

28. The fluorination method according to claim 16, wherein the fluorinating agent is obtained by mechanochemical treatment of a fluorine-containing compound and a base.

29. The fluorination method according to claim 15 or 16, further comprising the step of purifying the crude product obtained by fluorination to recover the fluorinated target.

30. The fluorination method according to claim 15 or 16, wherein the fluorination is carried out by a dry process.

31. The fluorination method according to claim 15 or 16, wherein the fluorination is performed by mechanochemical treatment of the fluorinating agent and the object to be fluorinated.

32. The fluorination method according to claim 15 or 16, wherein the step of obtaining the fluorinating agent and the step of fluorinating are carried out in succession.

33. The fluorination method according to claim 15 or 16, wherein the amount of the fluorinating agent used is 1.0 to 3.0 equivalents per equivalent of a group that can be substituted with a fluorine atom in the object.

34. The fluorination method according to claim 15 or 16, wherein the object is an organic compound having at least one selected from the group consisting of chlorine atoms and bromine atoms.

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