Composition production method, fluorination method, and composition

Abstract

To provide a composition production method with which a composition containing fluoride ions can be obtained from a fluorine-containing compound by means of a general-purpose device; a fluorination method using the composition; and a novel composition.SOLUTION: The present disclosure pertains to a composition production method comprising a step for obtaining a composition containing fluoride ions by causing a fluorine-containing compound to react by performing a mechanochemical treatment on the fluorine-containing compound and at least one selected from the group consisting of organic bases, reducing agents, and proton sources.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to a method for producing a composition, a fluorination method, and a composition. [Background technology]

[0002] A method for defluorinating polyvinylidene fluoride by mechanochemical treatment using a planetary mill in the presence of sodium hydroxide is known (see, for example, Patent Document 1). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2001-253969 Summary of the Invention [Problem to be solved by the invention]

[0004] An object of the present disclosure is to provide a method for producing a composition that can obtain a composition containing fluoride ions from a fluorine-containing compound using a general-purpose device, a fluorination method that uses the composition, and a novel composition. [Means for solving the problem]

[0005] The present disclosure (1) is a method for producing a composition, comprising a step of mechanochemically treating a fluorine-containing compound with at least one selected from the group consisting of an organic base, a reducing agent, and a proton source to react the fluorine-containing compound, thereby obtaining a composition containing fluoride ions.

[0006] The present disclosure (2) is the production method according to the present disclosure (1), wherein the organic base has a pKa of 8 to 40.

[0007] The present disclosure (3) is directed to a method for preparing a hydroxyl group-containing organic base, wherein the organic base is selected from the group consisting of alkali metals, alkaline earth metals, and NR 1 4(R 1may be the same or different, and contain at least one selected from the group consisting of H or an organic group having 1 to 10 carbon atoms).

[0008] The present disclosure (4) is directed to a method for treating a hydroxyl group comprising administering to a subject the organic base, 10 OM (in the formula, R 10 is 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 represent H or an organic group having 1 to 10 carbon atoms.) The present invention is a method for producing an arbitrary combination of a compound represented by any one of the present disclosures (1) to (3).

[0009] The present disclosure (5) is a method for producing any combination of the present disclosures (1) to (4), in which the organic base is at least one selected from the group consisting of sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide, sodium t-butoxide, and potassium t-butoxide.

[0010] The present disclosure (6) is a production method for any combination with any of the present disclosures (1) to (5), in which the amount of the organic base used is 0.10 to 3 equivalents per equivalent of the fluorine-containing compound.

[0011] The present disclosure (7) is a production method for any combination with any of the present disclosures (1) to (6), in which the standard electrode potential of the reducing agent is −0.44 V or less.

[0012] The present disclosure (8) is a method for producing any combination of the present disclosures (1) to (7), in which the reducing agent is at least one selected from the group consisting of Zn, Fe, Al, alkali metals, and alkaline earth metals.

[0013] The present disclosure (9) is a method for producing any combination of the present disclosures (1) to (8), in which the reducing agent is at least one selected from the group consisting of alkali metals and alkaline earth metals.

[0014] The present disclosure (10) is a method for producing any combination of the present disclosures (1) to (9), in which the reducing agent is at least one selected from the group consisting of Li, Na, K, Mg, and Ca.

[0015] The present disclosure (11) is a method for producing any combination of the present disclosures (1) to (10), in which the reducing agent is at least one selected from the group consisting of K and Ca.

[0016] The present disclosure (12) is a production method for any combination with any of the present disclosures (1) to (11), in which the amount of the reducing agent used is 0.7 to 20 equivalents per equivalent of the fluorine-containing compound.

[0017] The present disclosure (13) is a method for producing an arbitrary combination of any of the present disclosures (1) to (12), in which the proton source is at least one selected from the group consisting of amines and alcohols.

[0018] The present disclosure (14) is a method for producing any combination of the present disclosures (1) to (13), in which the proton source is at least one selected from the group consisting of ethylenediamine, methanol, ethanol, t-butyl alcohol, and 1-adamantanol.

[0019] The present disclosure (15) is a method for producing any combination of the present disclosures (1) to (14) in which the proton source is a primary amine.

[0020] The present disclosure (16) is a method for producing an arbitrary combination of the present disclosures (1) to (15) in which the proton source is ethylenediamine.

[0021] The present disclosure (17) is a production method for any combination with any of the present disclosures (1) to (16), in which the amount of the proton source used is 8 to 50 equivalents per equivalent of the fluorine-containing compound.

[0022] The present disclosure (18) is a method for producing any combination of the present disclosures (1) to (17), in which the fluorine-containing compound and the organic base are subjected to a mechanochemical treatment.

[0023] The present disclosure (19) is a method for producing any combination of the present disclosures (1) to (17), in which the fluorine-containing compound and the reducing agent are subjected to a mechanochemical treatment.

[0024] The present disclosure (20) is a method for producing any combination of any of the present disclosures (1) to (17), which comprises mechanochemically treating the fluorine-containing compound, the reducing agent, and the proton source.

[0025] The present disclosure (21) is a method for producing an arbitrary combination of the present disclosures (1) to (20) in which the fluorine-containing compound is solid at 25°C.

[0026] The present disclosure (22) is a method for producing an arbitrary combination of the present disclosures (1) to (21) in which the fluorine-containing compound is a fluorine-containing polymer.

[0027] The present disclosure (23) is a method for producing any combination of the present disclosures (1) to (22), in which the fluorine-containing compound is a fluorine-containing polymer containing polymerization units based on at least one monomer selected from the group consisting of tetrafluoroethylene, difluoroethylene, chlorotrifluoroethylene, hexafluoropropylene, perfluoro(alkyl vinyl ether), trifluoroethylene, and monofluoroethylene.

[0028] The present disclosure (24) is a method for producing any combination of the present disclosures (1) to (23), in which the fluorine-containing compound is at least one selected from the group consisting of perfluororesins and polydifluoroethylenes.

[0029] The present disclosure (25) is a method for producing any combination of the present disclosures (1) to (24), in which the fluorine-containing compound is at least one selected from the group consisting of polytetrafluoroethylene and polydifluoroethylene.

[0030] The present disclosure (26) is a method for producing any combination of the present disclosures (1) to (25), in which the fluorine-containing compound is at least one selected from the group consisting of polytetrafluoroethylene, polyvinylidene fluoride, and polychlorotrifluoroethylene.

[0031] The present disclosure (27) is a fluorination method including a step of fluorinating an object using a composition containing fluoride ions obtained by a production method in any combination with any of the present disclosures (1) to (26).

[0032] The present disclosure (28) is the fluorination method according to the present disclosure (27), in which the fluorination is carried out by a dry method.

[0033] The present disclosure (29) is the fluorination method according to the present disclosure (27) or (28), in which the fluorination is carried out by mechanochemically treating the composition and the object.

[0034] The present disclosure (30) is a fluorination method in any combination with any of the present disclosures (27) to (29), in which the step of obtaining the composition and the step of fluorination are carried out continuously.

[0035] The present disclosure (31) is a fluorination method in any combination with any of the present disclosures (27) to (30), in which the amount of the composition used is 1.0 to 3.0 equivalents per equivalent of a group that can be substituted with a fluorine atom that the object has.

[0036] The present disclosure (32) is a fluorination method in any combination with any of the present disclosures (27) to (31), in which the target substance is an organic compound having at least one atom selected from the group consisting of a chlorine atom and a bromine atom.

[0037] The present disclosure (33) is a composition containing fluoride ions and a carbon-based substance and / or a polyolefin having a fluorine content of 10 mass % or less.

[0038] The present disclosure (34) is the composition according to the present disclosure (33), wherein the carbon-based substance is amorphous carbon.

[0039] The present disclosure (35) is the composition according to the present disclosure (33) or (34), wherein the polyolefin is polyethylene.

[0040] The present disclosure (36) is a composition in any combination with any of the present disclosures (33) to (35), in which the content of the fluoride ions is 1 to 30 mass %.

[0041] The present disclosure (37) is a composition that is an arbitrary combination with any of the present disclosures (33) to (36) and that does not substantially contain fluororesin.

[0042] The present disclosure (38) is a composition of any combination with any of the present disclosures (33) to (37) which are fluorinating agents. [Effects of the Invention]

[0043] According to the present disclosure, it is possible to provide a method for producing a composition that can obtain a composition containing fluoride ions from a fluorine-containing compound using a general-purpose device, a fluorination method that uses the composition, and a novel composition. DETAILED DESCRIPTION OF THE INVENTION

[0044] The present disclosure will be specifically described below.

[0045] The present disclosure relates to a method for producing a composition, which includes a step of subjecting a fluorine-containing compound to mechanochemical treatment with at least one selected from the group consisting of an organic base, a reducing agent, and a proton source to react with the fluorine-containing compound, thereby obtaining a composition containing fluoride ions.

[0046] In the production method of the present disclosure, a composition containing fluoride ions can be obtained from a fluorine-containing compound using a general-purpose device with relatively low energy consumption by carrying out a mechanochemical treatment using at least one selected from the group consisting of an organic base, a reducing agent, and a proton source. Furthermore, since the mechanochemical treatment does not require high energy consumption, wear particles derived from the device are less likely to be generated, and a composition with few impurities can be obtained.

[0047] In the production method of the present disclosure, any one of an organic base, a reducing agent, and a proton source may be used, or two or more of them may be used in combination. As will be described later, main embodiments of the production method of the present disclosure include a method comprising mechanochemical treatment of a fluorine-containing compound and an organic base (hereinafter also referred to as production method (1) of the present disclosure), a method comprising mechanochemical treatment of a fluorine-containing compound and a reducing agent (hereinafter also referred to as production method (2-1) of the present disclosure), and a method comprising mechanochemical treatment of a fluorine-containing compound, a reducing agent, and a proton source (hereinafter also referred to as production method (2-2) of the present disclosure). In this specification, unless otherwise specified, production methods (1), (2-1), and (2-2) of the present disclosure will be collectively referred to as the "production method of the present disclosure." Furthermore, the compositions of the present disclosure described below can be produced by the production methods (2-1) and (2-2) of the present disclosure.

[0048] <Manufacturing method (1) of the present disclosure> In the production method (1) of the present disclosure, a fluorine-containing compound and an organic base are subjected to a mechanochemical treatment. The fluorine-containing compound used in the production method of the present disclosure may be any compound having a fluorine atom, may be a compound having a fluorine atom bonded to a carbon atom, and is preferably an organic compound having a fluorine atom bonded to a carbon atom. The fluorine-containing compound is preferably a solid at 25° C., since this facilitates mechanochemical treatment.

[0049] The fluorine-containing compound is preferably a fluorine-containing polymer compound, more preferably a fluorine-containing polymer.

[0050] The fluorine-containing polymer preferably contains polymerized 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 difluoroethylene include vinylidene fluoride [VdF] and 1,2-difluoroethylene. The fluoropolymer more preferably contains polymerization units based on at least one monomer selected from the group consisting of TFE, difluoroethylene and CTFE, further preferably contains polymerization units based on at least one monomer selected from the group consisting of TFE, VdF and CTFE, still 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.

[0051] The fluorine-containing polymer may be a fluororesin or a fluororubber.

[0052] Examples of the fluororesin 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, and Et / CTF Examples of the perfluoroalkyl allyl ether include CF₂═CF₂═CF₂═O-Rf copolymer, polyvinyl fluoride [PVF], polydifluoroethylene, 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, and TFE / perfluoroalkyl allyl ether copolymer, which can be used alone or in combination. The perfluoroalkyl allyl ether is CF₂═CF₂═O-Rf 1 (Rf 1 is a monomer represented by a perfluoroalkyl group having 1 to 5 carbon atoms.

[0053] Examples of the fluororubber 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, and these may be used alone or in combination.

[0054] Examples of the 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 / copolymer of a fluorine-containing monomer represented by the following formula (1): Formula (1): CH2=CFRf 2 (1) (In the formula, Rf 2 is a linear or branched fluoroalkyl group having 1 to 12 carbon atoms)

[0055] The fluoropolymer 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, still more preferably at least one selected from the group consisting of PTFE and PVdF, and particularly preferably PVdF. The fluorine-containing polymer is also preferably a perhalogen resin, more preferably at least one selected from the group consisting of a perfluororesin and PCTFE, even more preferably at least one selected from the group consisting of PTFE, PFA, FEP and PCTFE, and even more preferably at least one selected from the group consisting of PTFE, PFA and FEP. The fluorine-containing polymer is preferably at least one selected from the group consisting of perfluororesins and polydifluoroethylene, and more preferably at least one selected from the group consisting of PTFE and polydifluoroethylene.

[0056] The fluorine-containing compound does not have to be a polymer, and may be a fluorine-containing low molecular weight compound, as long as it is solid at 25° C. The fluorine-containing low molecular weight compound is represented 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 of 4 or more, y1 represents an integer of 0 to 3, and A represents -CF(CF3)2OM I , -PO(OM I )2, -SO3M I or -COOM I indicates M I represents H, NH4, Li, Na, Mg, Al, K or Ca), and a compound (I) represented by the following general formula (II): F-(CF2) X2 O(CFXCF2O) y2 -CFX-A (II) (In the formula, x2 represents an integer of 1 or more, y2 represents an integer of 0 to 10, X represents F or CF3, and A represents -SO3M II or -COOM II indicates M II represents H, NH4, Li, Na, Mg, Al, K or Ca.

[0057] The compound (I) includes fluorocarboxylic acids and their salts, preferably perfluorocarboxylic acids and their salts, such as perfluorooctanoic acid and its salts (collectively referred to as "PFOA"), perfluorohexanoic acid and its salts, and perfluorobutanoic acid and its salts. Examples of the salts include ammonium salts and sodium salts, and preferably ammonium salts, such as ammonium perfluorooctanoate (particularly referred to as "APFO"). Compound (I) also includes 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 the salts include ammonium salts and sodium salts. Examples of the compound (II) include perfluoroethercarboxylic acids and salts thereof, such as 2,3,3,3-tetrafluoro-2-[1,1,2,3,3,3-hexafluoro-2-(trifluoromethoxy)propoxy]-propanoic acid.

[0058] The fluorine-containing low molecular weight compound may be adsorbed onto an adsorbent. In this embodiment, the solid in which the fluorine-containing low molecular weight compound is adsorbed onto the adsorbent may be subjected to mechanochemical treatment. The adsorbent is not limited as long as it is a solid capable of adsorbing the fluorine-containing low-molecular-weight compound, but is preferably at least one selected from the group consisting of activated carbon, silica gel, clay, metal-organic framework (MOF), and zeolite.

[0059] A raw material composition containing the above-mentioned fluorine-containing compound and other components may be subjected to mechanochemical treatment. The other components can be used within a range that does not impair the effects of the present disclosure. Examples of the other components include general fillers and polymers, and the above-mentioned adsorbents.

[0060] Examples of the common filler include inorganic fillers such as glass fiber, glass beads, carbon fiber, 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.

[0061] Examples of the 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 polyether ether ketone (PEEK); polyamide-imide (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 nylon MXD6 is a crystalline polycondensate obtained from metaxylenediamine (MXD) and adipic acid. The general polymers may be non-fluorinated polymers.

[0062] The content of the other components may be 50% by mass or less, preferably 30% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less, relative to the raw material composition, 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.

[0063] The fluorine-containing compound (or the raw material composition when the other components are present) may be in the form of a powder, a molded product, or waste material from the manufacturing process or after use of a product. It may also be one that has been heated once to a temperature above its melting point. If necessary, the fluorine-containing compound may be pulverized before use. From the viewpoint of reaction efficiency, a smaller particle size is preferred.

[0064] The organic base used in the production method (1) of the present disclosure is a basic organic compound, preferably a strongly basic organic compound, and is preferably a solid at 25°C, in order to facilitate mechanochemical treatment.

[0065] The organic base preferably has a pKa (acid dissociation constant in water at 25°C) of 40 or less, more preferably 35 or less, and even more preferably 20 or less, and preferably 8 or more, more preferably 9 or more, more preferably 12 or more, and even more preferably 15 or more, in order to facilitate mechanochemical treatment using a general-purpose device. The pKa is determined by neutralization titration.

[0066] The organic base is a metal and NR 1 4(R 1 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 metal include monovalent and divalent metals, such as alkali metals (Group 1) and alkaline earth metals (Group 2), and specific examples include Na, K, Li, Ca, etc. Of these, alkali metals are preferred, Na and K are more preferred, and K is even more preferred. NR 1 4 is ammonium (unsubstituted or substituted ammonium), and the four R 1 may be the same or different. R 1 is preferably H or an organic group having 1 to 10 carbon atoms, more preferably H or an organic group having 1 to 4 carbon atoms.

[0067] The organic bases include alkali metals, alkaline earth metals, and NR 1 4(R 1may be the same or different, and more preferably contain at least one selected from the group consisting of H or an organic group having 1 to 10 carbon atoms, even more preferably contain at least one selected from the group consisting of alkali metals and alkaline earth metals, even more preferably contain an alkali metal, even more preferably contain at least one selected from the group consisting of Na and K, and particularly preferably contain K.

[0068] The organic base may be R 10 OM (in the formula, R 10 is 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 represent H or an organic group having 1 to 10 carbon atoms). Examples of the compound represented by the formula (I), metal acetates, cyclic amines, polyamines, etc. R 10 The number of carbon atoms in the organic group R is preferably 2 or more, more preferably 3 or more, and is preferably 8 or less, more preferably 6 or less. 10 As the alkyl group, an alkyl group having a carbon number within the above range is preferred, and a t-butyl group is more preferred. M metal and NR 1 Examples of 4 include those mentioned above. M is preferably a metal, more preferably an alkali metal or alkaline earth metal, even more preferably an alkali metal, even more preferably Na or K, and particularly preferably K. The metal of the metal acetate is preferably an alkali metal or alkaline earth metal, more preferably an alkali metal, even more preferably Na or K, and particularly preferably K. Examples of the cyclic amine include 1,8-diazabicyclo[5.4.0]-7-undecene (DBU) and derivatives thereof. Examples of the polyamine include polyethyleneimine.

[0069] As the organic base, R is preferred because it makes mechanochemical treatment easier using general-purpose equipment. 10At least one selected from the group consisting of compounds represented by OM and metal acetates is 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 methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide, sodium t-butoxide, and potassium t-butoxide is particularly preferred.

[0070] The amount of the organic base used in the mechanochemical treatment in the production method (1) of the present disclosure is preferably 0.01 equivalents or more, more preferably 0.05 equivalents or more, and even more preferably 0.10 equivalents or more, relative to 1 equivalent (molar equivalent) of the fluorine-containing compound, and is 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. In the production method (1) of the present disclosure, the mechanochemical treatment can be carried out with a relatively small amount of organic base, which has the advantage of facilitating purification and reducing the impact on the fluorination yield. When the fluorine-containing compound is a fluorine-containing polymer, the equivalent weight is calculated based on the monomers constituting the fluorine-containing polymer.

[0071] Mechanochemical processing is a processing method in which mechanical energy is applied to a reactant (preferably a solid reactant) by methods such as shearing, compression, stretching, grinding, friction, kneading, mixing, dispersing, crushing, and shaking, thereby activating the reactant and imparting structural change, phase transition, reactivity, adsorption, catalytic activity, etc. The mechanochemical treatment method is not particularly limited, and examples thereof include a compressive shear treatment method, an impact treatment method, and a mixed shear friction method, with the impact treatment method being preferred.

[0072] The apparatus for carrying out the mechanochemical treatment is not particularly limited as long as it is an apparatus capable of applying mechanical energy by the above-mentioned method, and known pulverizers and mixers can be used. For example, pulverizers such as ball mills, rod mills, jet mills, vibration mills, and SAG mills; grinders such as rotary stone mills and crushers; (horizontal axis rotation) container rotation type mixers such as horizontal cylindrical, V-type, double cone, square cube, S-type, and continuous V-type; (baffle blade equipped) container rotation type mixers such as horizontal cylindrical, V-type, double cone, and ball mill types; (rotation vibration) container rotation type mixers such as rocking type and cross rotary type; (horizontal axis) container rotation type mixers such as ribbon type, paddle type, single shaft rotor type, and bag mill type. (rotating) fixed vessel type mixers; (vertical axis rotating) fixed vessel type mixers such as ribbon type, screw type, planetary type, turbine type, high speed fluid type, rotating disk type and Mahler type; (vibrating) fixed vessel type mixers such as vibration mill type and sieve; (fluidization) fluid motion type mixers such as heterogeneous fluidized bed, swirling fluidized bed, type with riser and Jot pump type; (gravity) fluid motion type mixers such as gravity type and static mixer; kneaders such as twin-screw kneaders, single-screw kneaders, mixers, roll mills, etc.

[0073] As the device for carrying out the mechanochemical treatment, a device using balls is preferred, and a ball mill (excluding planetary ball mills) is more preferred.

[0074] The mechanochemical treatment in the manufacturing method (1) of the present disclosure preferably does not use a planetary mill. While a planetary mill is a device capable of applying high energy, it also generates a large amount of wear debris. 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 rotation speed of a planetary mill and the amount of wear debris generated from the device, and shows that a certain amount of wear debris is generated at 700 rpm, the rotation speed adopted in the aforementioned Patent Document 1. The inclusion of wear debris may interfere with the use of the composition after the reaction. If the composition after the reaction is to be used for purposes such as fluorination, it is preferable that it does not contain impurities. The manufacturing method of the present disclosure allows the reaction of a fluorinated compound under conditions that are less likely to generate wear debris from the device, allowing the resulting composition to be used as a fluorinating agent, etc. Furthermore, the method using a general-purpose device such as a ball mill instead of a planetary mill has the advantage of being easily industrialized.

[0075] The temperature of the mechanochemical treatment in the manufacturing method (1) of the present disclosure 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 is preferably 300°C or lower, more preferably 250°C or lower, even more preferably 200°C or lower, even more preferably 160°C or lower.

[0076] In particular, when the fluorine-containing compound is a fluorine-containing polymer compound that does not contain hydrogen, the reaction is accelerated by heating, so it is preferable to carry out the reaction at room temperature (25° C.) or above.

[0077] When the mechanochemical treatment in production method (1) of the present disclosure is carried out using a ball mill (excluding planetary ball mills), the shaking conditions can be determined depending on the apparatus and ball used. For example, when treatment is carried out using a jar of about 1 to 20 mL and one stainless steel ball of about 1 to 15 mm in diameter, shaking can be carried out under conditions of preferably 100 rpm or more, more preferably 300 rpm or more, even more preferably 500 rpm or more, and preferably 1800 rpm or less, more preferably 1600 rpm or less, even more preferably 1500 rpm or less. Alternatively, the heating may be performed under conditions of preferably 3 Hz or more, more preferably 5 Hz or more, even more preferably 10 Hz or more, and preferably 60 Hz or less, more preferably 50 Hz or less, even more preferably 30 Hz or less.

[0078] When the mechanochemical treatment in the manufacturing method (1) of the present disclosure is carried out using a ball mill (excluding a planetary ball mill), the time for the mechanochemical treatment is preferably 5 minutes or more, more preferably 10 minutes or more, and even more preferably 20 minutes or more, and is 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.

[0079] The mechanochemical treatment in the production method (1) of the present disclosure may be carried out in any atmosphere, for example, in air, in an inert gas, in vacuum, etc. From the viewpoint of low cost, it is preferably carried out in air.

[0080] The mechanochemical treatment in the production method (1) of the present disclosure 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 facilitate mixing of the components. The amount of the solvent used is preferably 0.001 μl / mg or more, more preferably 0.01 μl / mg or more, and even more preferably 0.05 μl / mg or more, based on the total mass of the fluorine-containing compound and the organic base, and is 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. In the production method (1) of the present disclosure, the solvent refers to a liquid medium that does not react with the fluorine-containing compound and the organic base.

[0081] As the solvent for the mechanochemical treatment in the production method (1) of the present disclosure, organic solvents such as ether-based, nitrile-based, ester-based, aromatic, hydrocarbon-based, alcohol-based, and halogen-based organic solvents are preferred. Examples of the organic solvent 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, isopropanol, and ethylene glycol monoalkyl ether; 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, and mixtures thereof. Of these, cyclic ethers are preferred as the solvent.

[0082] The mechanochemical treatment in the production method (1) of the present disclosure is preferably carried out in a dry manner, which 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.

[0083] In the production method (1) of the present disclosure, the fluorine-containing compound can be reacted by a mechanochemical treatment. The reaction may be a reaction that produces fluoride ions, and is preferably a defluorination reaction.

[0084] The mechanochemical treatment in the manufacturing method (1) of the present disclosure provides a composition containing fluoride ions. The content of fluoride ions in the composition 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, and particularly preferably 5.0% by mass or more, and is preferably 50% by mass or less, more preferably 30% by mass or less, even more preferably 20% by mass or less, and particularly preferably 15% by mass or less, and may be 10% by mass or less.

[0085] The composition obtained by the production method (1) of the present disclosure usually contains counterions together with fluoride ions. The counterions include metal and NR 1 4(R 1 may be the same or different, and are preferably 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. 1 Examples of 4 include those mentioned above. The counter ion is preferably a metal, more preferably an alkali metal or alkaline earth metal, even more preferably an alkali metal, even more preferably Na or K, and particularly preferably K.

[0086] The content of the counter ions is preferably an amount that balances the charge of the fluoride ions.

[0087] The composition obtained by the production method (1) of the present disclosure may contain a compound having a fluoride ion, or may contain a compound having a fluoride ion and a counter ion. Examples of the compound include metal fluorides and ammonium fluoride, with metal fluorides being preferred, alkali metal fluorides being more preferred, and potassium fluoride being even more preferred.

[0088] The composition obtained by the production method (1) of the present disclosure may contain a fluorine-containing compound. Examples of the fluorine-containing compound in the composition include the same fluorine-containing compounds as those used in the mechanochemical treatment described above. The fluorine-containing compound in the composition may be an unreacted raw material.

[0089] The content of the fluorine-containing compound in the composition obtained by Production Method (1) of the present disclosure is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and even more preferably 0.5% by mass or more, and is 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. The content of the fluorine-containing compound is preferably as small as possible.

[0090] The composition obtained by the production method (1) of the present disclosure is preferably substantially free of fluorine-containing organic compounds. "Substantially free of fluorine-containing organic compounds" means that the content of organic fluorine in the composition 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 organic fluorine in the fluorinating agent is measured by combustion ion chromatography. The organic fluorine refers to fluorine bonded to carbon.

[0091] The composition obtained by the production method (1) of the present disclosure may contain an organic base. Examples of the organic base in the composition include the same organic bases as those used in the mechanochemical treatment described above. The organic base in the composition may be an unreacted raw material.

[0092] The content of the organic base in the composition obtained by production method (1) of the present disclosure is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and even more preferably 0.1% by mass or more, and is 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 the organic base is within the above range, decomposition of the substrate in the subsequent fluorination step can be prevented, which is preferable from the viewpoint of yield.

[0093] The composition obtained by the production method (1) of the present disclosure preferably contains a compound having a structure in which the above-mentioned fluorine-containing compound has been defluorinated (by mechanochemical treatment). The compound may have a structure in which at least some of the fluorine atoms in the above-mentioned fluorine-containing compound have been defluorinated. The compound is a compound in which at least some of the fluorine atoms of the fluorine-containing compound have a structure derived from the organic base, for example, R 10 O-(R 10 is the same as above) (preferably an alkoxy group). Whether the composition contains a compound having the above structure can be confirmed by removing components other than the fluorine-containing compound from the composition by washing or the like, and then analyzing the composition by XPS, FT-IR, solid-state NMR or the like, and by measuring the carbon and fluorine contents before and after the reaction by elemental analysis.

[0094] The composition obtained by production method (1) of the present disclosure is preferably a solid at 25° C., and more preferably a powder, in view of ease of handling.

[0095] The composition obtained by production method (1) of the present disclosure has a maximum particle size that can be confirmed when observed with a microscope such as a video microscope, of preferably 7 mm or less, more preferably 6 mm or less, even more preferably 5 mm or less, and particularly preferably 4 mm or less, and 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. A composition having a maximum particle size within the above range does not form agglomerates and is easy to handle.

[0096] <Production method (2-1) of the present disclosure> In the production method (2-1) of the present disclosure, a fluorine-containing compound and a reducing agent are subjected to a mechanochemical treatment, whereby a composition containing fluoride ions can be obtained under relatively mild conditions. The production method (2-1) of the present disclosure is a method that does not use a proton source, which will be described later.

[0097] As the fluorine-containing compound in the production method (2-1) of the present disclosure, the same fluorine-containing compound as in the production method (1) of the present disclosure can be used.

[0098] The reducing agent in the production method (2-1) of the present disclosure may be any substance capable of reducing the above-mentioned fluorine-containing compound, but from the viewpoint of reactivity, the standard electrode potential is preferably −0.44 V or less, more preferably −0.72 V or less, more preferably −1.67 V or less, even more preferably −2.50 V or less, even more preferably −2.71 V or less, and preferably −3.50 V or more, more preferably −3.30 V or more, and even more preferably −3.10 V or more. The standard electrode potential is calculated, for example, by the method described in the 6th Revised Edition of the Chemical Handbook.

[0099] The reducing agent includes alkali metals, alkaline earth metals, and metals (elemental substances) such as Zn, Fe, and Al, and one or more of these can be used.

[0100] The alkali metals include Li, Na, K, etc., and among these, Li and K are preferred. The alkaline earth metals include Mg, Ca, Sr, etc., and among these, Mg and Ca are preferred, with Ca being more preferred.

[0101] The reducing agent is preferably a metal, more preferably at least one selected from the group consisting of alkali metals, alkaline earth metals, Zn, Fe, and Al, even more preferably at least one selected from the group consisting of Li, Na, K, Mg, Zn, Al, and Ca, even more preferably at least one selected from the group consisting of Li, Na, K, Mg, and Ca, even more preferably at least one selected from the group consisting of Li, Na, K, and Ca, even more preferably at least one selected from the group consisting of Li, Na, and K, and particularly preferably K. The reducing agent is preferably at least one selected from the group consisting of alkali metals and alkaline earth metals, and more preferably an alkali metal.

[0102] The amount of the reducing agent used in the production method (2-1) of the present disclosure is, relative to 1 equivalent (molar equivalent) of the fluorine-containing compound, preferably 0.01 equivalents or more, more preferably 0.05 equivalents or more, even more preferably 0.10 equivalents or more, even more preferably 0.50 equivalents or more, and particularly preferably 1 equivalent or more, and is preferably 20 equivalents or less, more preferably 10 equivalents or less, even more preferably 8 equivalents or less, even more preferably 5 equivalents or less, even more preferably 4 equivalents or less, even more preferably 3 equivalents or less, and particularly preferably 1.5 equivalents or less. In the production method (2-1) of the present disclosure, the mechanochemical treatment can be carried out with a relatively small amount of reducing agent, which has the advantage of preventing decomposition of the substrate in the fluorination step.

[0103] The mechanochemical treatment in the production method (2-1) of the present disclosure can be carried out using an apparatus similar to that described in the production method (1) of the present disclosure.

[0104] The temperature of the mechanochemical treatment in the manufacturing method (2-1) of the present disclosure 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 is preferably 200°C or lower, more preferably 150°C or lower, even more preferably 100°C or lower, even more preferably 50°C or lower, and particularly preferably 40°C or lower. In the production method (2-1) of the present disclosure, the mechanochemical treatment can be carried out at a relatively low temperature.

[0105] When the mechanochemical treatment in production method (2-1) of the present disclosure is carried out using a ball mill (excluding planetary ball mills), the shaking conditions can be determined depending on the apparatus and ball used. For example, when treatment is carried out using a jar of about 1 to 20 mL and one stainless steel ball of about 1 to 15 mm in diameter, shaking can be carried out under conditions of preferably 100 rpm or more, more preferably 300 rpm or more, even more preferably 500 rpm or more, and preferably 1800 rpm or less, more preferably 1600 rpm or less, even more preferably 1500 rpm or less. Alternatively, the heating may be performed under conditions of preferably 3 Hz or more, more preferably 5 Hz or more, even more preferably 10 Hz or more, and preferably 60 Hz or less, more preferably 50 Hz or less, even more preferably 30 Hz or less.

[0106] When the mechanochemical treatment in the manufacturing method (2-1) of the present disclosure is carried out using a ball mill (excluding a planetary ball mill), the time for the mechanochemical treatment is preferably 1 minute or more, more preferably 5 minutes or more, and even more preferably 10 minutes or more, and is preferably 500 minutes or less, more preferably 300 minutes or less, even more preferably 200 minutes or less, and even more preferably 60 minutes or less. In the production method (2-1) of the present disclosure, the mechanochemical treatment can be carried out in a relatively short time.

[0107] The mechanochemical treatment in the production method (2-1) of the present disclosure may be carried out in any atmosphere, for example, in air, in an inert gas, in vacuum, etc. From the viewpoint of low cost, it is preferably carried out in air.

[0108] The mechanochemical treatment in the production method (2-1) of the present disclosure 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 facilitate mixing of the components. The amount of the solvent used is preferably 0.001 μl / mg or more, more preferably 0.01 μl / mg or more, and even more preferably 0.05 μl / mg or more, based on the total mass of the fluorine-containing compound and the reducing agent, and is 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. However, in the production method (2-1) of the present disclosure, the reaction proceeds sufficiently even without a solvent, so it is preferable not to use a solvent. In the production method (2-1) of the present disclosure, the solvent refers to a liquid medium that does not react with the fluorine-containing compound and the reducing agent.

[0109] Solvents that can be used in the mechanochemical treatment in the production method (2-1) of the present disclosure include the solvents exemplified in the production method (1) of the present disclosure.

[0110] The mechanochemical treatment in the production method (2-1) of the present disclosure is preferably carried out in a dry system, which 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.

[0111] In the production method (2-1) of the present disclosure, the fluorine-containing compound can be reacted by a mechanochemical treatment. The reaction may be a reaction that produces fluoride ions, and is preferably a defluorination reaction.

[0112] The production method (2-1) of the present disclosure provides a composition containing fluoride ions. By performing mechanochemical treatment without using a proton source, a carbon-based substance mainly composed of carbon is produced together with fluoride ions, and for example, the composition (1) of the present disclosure described below is obtained.

[0113] <Production method (2-2) of the present disclosure> In the production method (2-2) of the present disclosure, a fluorine-containing compound, a reducing agent, and a proton source are subjected to mechanochemical treatment, whereby a composition containing fluoride ions can be obtained under relatively mild conditions.

[0114] As the fluorine-containing compound in the production method (2-2) of the present disclosure, the same fluorine-containing compound as in the production method (1) of the present disclosure can be used.

[0115] The reducing agent in the production method (2-2) of the present disclosure can be the same as the reducing agent in the production method (2-1) of the present disclosure, and the preferred forms are also the same. However, it is also preferable that the reducing agent is at least one selected from the group consisting of K, Li, and Ca, or at least one selected from the group consisting of K and Li, and Li is also preferable.

[0116] The amount of the reducing agent used in the production method (2-2) of the present disclosure is preferably 0.01 equivalents or more, more preferably 0.05 equivalents or more, even more preferably 0.10 equivalents or more, even more preferably 0.50 equivalents or more, and particularly preferably 1 equivalent or more, relative to 1 equivalent (molar equivalent) of the fluorine-containing compound, and is preferably 20 equivalents or less, more preferably 10 equivalents or less, even more preferably 8 equivalents or less, even more preferably 5 equivalents or less, even more preferably 4 equivalents or less, even more preferably 3 equivalents or less, and particularly preferably 2 equivalents or less. In the production method (2-2) of the present disclosure, the mechanochemical treatment can be carried out with a relatively small amount of reducing agent, which has the advantage of preventing decomposition of the substrate in the fluorination step.

[0117] The proton source in the production method (2-2) of the present disclosure may be any substance capable of supplying protons, but is preferably a substance different from the reducing agent described above, and more preferably an organic compound capable of supplying protons.

[0118] The proton source includes amines, alcohols, etc., and one or more of these can be used. The amine is preferably at least one selected from the group consisting of primary amines and secondary amines. Examples of the primary amine include monoamines such as methylamine and ethylamine; and diamines such as ethylenediamine and hexamethylenediamine. Examples of the secondary amine include dimethylamine, diethylamine, and diethylenetriamine. Of the above amines, diamines having a primary amino group are preferred, and ethylenediamine is more preferred. Examples of the alcohol include methanol, ethanol, n-propyl alcohol, t-butyl alcohol, and 1-adamantanol. Of these, t-butyl alcohol is preferred. Of these, the proton source is preferably at least one selected from the group consisting of ethylenediamine, t-butyl alcohol, and 1-adamantanol.

[0119] The amount of the proton source used in the production method (2-2) of the present disclosure is preferably 4 equivalents or more, more preferably 6 equivalents or more, and even more preferably 8 equivalents or more, relative to 1 equivalent (molar equivalent) of the fluorine-containing compound, and is preferably 100 equivalents or less, more preferably 80 equivalents or less, even more preferably 65 equivalents or less, even more preferably 50 equivalents or less, and particularly preferably 40 equivalents or less.

[0120] The mechanochemical treatment in the production method (2-2) of the present disclosure can be carried out using an apparatus similar to the apparatus described in the production method (1) of the present disclosure.

[0121] The temperature of the mechanochemical treatment in the manufacturing method (2-2) of the present disclosure 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 is preferably 200°C or lower, more preferably 150°C or lower, even more preferably 100°C or lower, even more preferably 50°C or lower, and particularly preferably 40°C or lower. In the production method (2-2) of the present disclosure, the mechanochemical treatment can be carried out at a relatively low temperature.

[0122] When the mechanochemical treatment in production method (2-2) of the present disclosure is carried out using a ball mill (excluding planetary ball mills), the shaking conditions can be determined depending on the apparatus and ball used. For example, when treatment is carried out using a jar of about 1 to 20 mL and one stainless steel ball of about 1 to 15 mm in diameter, shaking can be carried out under conditions of preferably 100 rpm or more, more preferably 300 rpm or more, even more preferably 500 rpm or more, and preferably 1800 rpm or less, more preferably 1600 rpm or less, even more preferably 1500 rpm or less. Alternatively, the heating may be performed under conditions of preferably 3 Hz or more, more preferably 5 Hz or more, even more preferably 10 Hz or more, and preferably 60 Hz or less, more preferably 50 Hz or less, even more preferably 30 Hz or less.

[0123] When the mechanochemical treatment in the manufacturing method (2-2) of the present disclosure is carried out using a ball mill (excluding a planetary ball mill), the time for the mechanochemical treatment is preferably 1 minute or more, more preferably 5 minutes or more, and even more preferably 10 minutes or more, and is preferably 600 minutes or less, more preferably 300 minutes or less, even more preferably 200 minutes or less, and even more preferably 60 minutes or less. In the production method (2-2) of the present disclosure, the mechanochemical treatment can be carried out in a relatively short time.

[0124] The mechanochemical treatment in the production method (2-2) of the present disclosure may be carried out in any atmosphere, for example, in air, in an inert gas, in vacuum, etc. From the viewpoint of low cost, it is preferably carried out in air.

[0125] The mechanochemical treatment in the production method (2-2) of the present disclosure 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 facilitate mixing of the components. The amount of the solvent used is preferably 0.001 μl / mg or more, more preferably 0.01 μl / mg or more, and even more preferably 0.05 μl / mg or more, based on the total mass of the fluorine-containing compound, the reducing agent, and the proton source, and is 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. However, in the production method (2-2) of the present disclosure, the reaction proceeds sufficiently even without a solvent, so it is preferable not to use a solvent. In the production method (2-2) of the present disclosure, the solvent refers to a liquid medium that does not react with the fluorine-containing compound, the reducing agent, and the proton source.

[0126] Solvents that can be used in the mechanochemical treatment in the production method (2-2) of the present disclosure include the solvents exemplified in the production method (1) of the present disclosure.

[0127] The mechanochemical treatment in the production method (2-2) of the present disclosure is preferably carried out in a dry manner, which 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.

[0128] In the production method (2-2) of the present disclosure, the fluorine-containing compound can be reacted by a mechanochemical treatment. The reaction may be a reaction that produces fluoride ions, and is preferably a defluorination reaction.

[0129] The production method (2-2) of the present disclosure provides a composition containing fluoride ions. By performing mechanochemical treatment using a proton source, a substance in which fluorine atoms in a fluorine-containing compound are substituted with hydrogen atoms is produced together with fluoride ions, and for example, the composition (2) of the present disclosure described below is obtained.

[0130] The production method of the present disclosure can react a fluorine-containing compound to obtain a composition containing fluoride ions, and can therefore be used to decompose (defluorinate) a fluorine-containing compound. The production method of the present disclosure can also be used to produce a compound having a fluoride ion. In this case, the composition obtained by the production method of the present disclosure may be purified to recover the compound having a fluoride ion. The production method of the present disclosure can also be used to produce a fluorinating agent. In this case, the composition obtained by the production method of the present disclosure can be used as a fluorinating agent as it is, or a purified compound having fluoride ions can be used as a fluorinating agent.

[0131] <Composition of the present disclosure> The composition of the present disclosure is a composition containing fluoride ions and a carbon-based substance and / or a polyolefin having a fluorine content of 10% by mass or less.

[0132] The composition of the present disclosure contains a carbon-based substance and / or a polyolefin having a fluorine content of 10% by mass or less together with fluoride ions, which can suppress moisture absorption by the composition and contribute to the stability of the composition.

[0133] The content of fluoride ions in the composition of the present disclosure may be 1% by mass or more, 5% by mass or more, 10% by mass or more, 15% by mass or more, or 20% by mass or more, and may be 70% by mass or less, 65% by mass or less, 60% by mass or less, 55% by mass or less, 50% by mass or less, 45% by mass or less, 40% by mass or less, 35% by mass or less, or 30% by mass or less. When the composition contains a proton source, the content is calculated as a percentage of the total amount excluding the proton source.

[0134] The composition of the present disclosure usually contains a counter ion together with a fluoride ion. The counter ion is preferably a metal, more preferably at least one selected from the group consisting of alkali metals, alkaline earth metals, Zn, Fe, and Al, even more preferably at least one selected from the group consisting of Li, Na, K, Mg, Zn, Al, and Ca, even more preferably at least one selected from the group consisting of Li, Na, K, Mg, and Ca, and even more preferably at least one selected from the group consisting of Li, Na, K, and Ca. The counter ion is preferably at least one selected from the group consisting of alkali metals and alkaline earth metals, and more preferably an alkali metal. When the composition of the present disclosure contains a carbon-based substance, at least one selected from the group consisting of Li, Na, and K is preferred, with K being particularly preferred. When the composition of the present disclosure contains a polyolefin, among these, at least one selected from the group consisting of Li, K, and Ca is even more preferable, and Li is particularly preferable. These may be included as cations.

[0135] The content of the counter ions is preferably an amount that balances the charge of the fluoride ions.

[0136] The composition of the present disclosure may contain a compound having a fluoride ion, or may contain a compound having a fluoride ion and a counter ion. The compound is preferably a metal fluoride, more preferably at least one selected from the group consisting of zinc fluoride, iron fluoride, aluminum fluoride, alkali metal fluorides, and alkaline earth metal fluorides, and even more preferably at least one selected from the group consisting of zinc fluoride, aluminum fluoride, lithium fluoride, sodium fluoride, potassium fluoride, magnesium fluoride, and calcium fluoride. When the composition of the present disclosure contains a carbon-based substance, among them, at least one selected from the group consisting of lithium fluoride, sodium fluoride, potassium fluoride, and calcium fluoride is preferable, at least one selected from the group consisting of lithium fluoride, sodium fluoride, and potassium fluoride is more preferable, and potassium fluoride is particularly preferable. When the composition of the present disclosure contains a polyolefin, among them, at least one selected from the group consisting of lithium fluoride, potassium fluoride, and calcium fluoride is preferred, with lithium fluoride being particularly preferred.

[0137] When the composition of the present disclosure contains KF, the content of KF in the composition may be 10% by mass or more, 15% by mass or more, 20% by mass or more, or 25% by mass or more, and may be 97% by mass or less, 95% by mass or less, or 91% by mass or less. A composition containing KF can be obtained, for example, by using K in the production method (2-1) of the present disclosure described above.

[0138] When the composition of the present disclosure contains LiF, the content of LiF in the composition may be 1% by mass or more, 2% by mass or more, 3% by mass or more, or 4% by mass or more, and may be 97% by mass or less, 95% by mass or less, or 91% by mass or less. The composition containing LiF can be obtained, for example, by using Li in the production method (2-1) of the present disclosure described above.

[0139] When the composition of the present disclosure contains NaF, the content of NaF in the composition may be 5% by mass or more, 10% by mass or more, 15% by mass or more, or 20% by mass or more, and may be 97% by mass or less, 95% by mass or less, or 91% by mass or less. The composition containing NaF can be obtained, for example, by using Na in the production method (2-1) of the present disclosure described above.

[0140] The carbon-based substance is a substance mainly composed of carbon. The carbon content of the carbon-based substance is preferably 20% by mass or more, more preferably 30% by mass or more, even more preferably 40% by mass or more, even more preferably 50% by mass or more, and particularly preferably 99.9% by mass or more. The upper limit is not particularly limited, and may be 100% by mass, 99.999% by mass, 90% by mass, or 80% by mass. The carbon content is measured by CHN analysis.

[0141] The carbon-based substance may or may not contain elements other than carbon, such as fluorine. The carbon-based substance may have a structure obtained by defluorinating a fluorine-containing compound (preferably a fluorine-containing polymer, more preferably a fluorine resin). The carbon-based material may be amorphous carbon.

[0142] The content of the carbon-based material in the composition of the present disclosure may be 5% by mass or more, 7% by mass or more, or 8% by mass or more, and may be 50% by mass or less, 40% by mass or less, or 30% by mass or less.

[0143] The polyolefin is a compound having repeating units based on olefins. Examples of the olefins include ethylene and propylene. The repeating units may be of one type or two or more types. The olefin is preferably ethylene or a combination of ethylene and propylene, and more preferably ethylene. The polyolefin is preferably at least one selected from the group consisting of polyethylene and ethylene propylene copolymer, and more preferably polyethylene.

[0144] The polyolefin may have a repeating unit corresponding to a structure obtained by polymerizing an olefin, and does not necessarily have to be one obtained by actually polymerizing an olefin. The polyolefin may further have a structure other than the repeating unit based on an olefin. The polyolefin may have a structure obtained by defluorinating and hydrogenating a fluorine-containing polymer (preferably a fluororesin).

[0145] The polyolefin has a fluorine content of 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 amount of fluorine in the polymer is measured by combustion ion chromatography.

[0146] The content of the polyolefin in the composition of the present disclosure may be 3% by mass or more, 5% by mass or more, or 8% by mass or more, based on the total amount excluding the proton source, and may be 50% by mass or less, 40% by mass or less, or 30% by mass or less.

[0147] The composition of the present disclosure is preferably substantially free of fluororesin. "Substantially free of fluororesin" means that the content of organic fluorine in the composition of the present 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. When the composition contains a proton source, the content is calculated as a percentage of the total amount excluding the proton source. The content of organic fluorine in the composition is measured by combustion ion chromatography. In this case, the fluororesin refers to a resin with a fluorine content of more than 10% by mass. The method for measuring the fluorine content in a polymer is as described above. Moreover, organic fluorine means fluorine bonded to carbon. When the composition is subjected to NMR analysis and no fluororesin is detected, it can be said that the composition does not substantially contain fluororesin.

[0148] It is also preferred that the composition of the present disclosure is substantially free of fluorine-containing polymers. "Substantially free of fluorine-containing polymers" means that the content of organic fluorine in the composition of the present disclosure is 10% by mass or less, preferably 5% by mass or less, preferably 3% by mass or less, more preferably 2% by mass or less, even more preferably 1% by mass or less, and even more 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. When the composition contains a proton source, the content is calculated as a percentage of the total amount excluding the proton source. In this case, the fluorine-containing polymer refers to a polymer having a fluorine content of more than 10% by mass. When the composition is subjected to NMR analysis and no fluorine-containing polymer is detected, it can also be said that the composition does not substantially contain a fluorine-containing polymer.

[0149] As described above, the composition of the present disclosure is preferably substantially free of fluororesin or fluoropolymer, but may contain fluororesin or fluoropolymer since these do not adversely affect the fluorination step described below. If necessary, the content of fluororesin or fluoropolymer can be adjusted by purification.

[0150] The composition of the present disclosure is preferably a solid at 25°C, and is preferably a powder, in view of ease of handling.

[0151] The composition of the present disclosure containing the carbon-based substance can be produced by the production method (2-1) of the present disclosure described above.

[0152] The composition of the present disclosure containing the polyolefin can be produced by the production method (2-2) of the present disclosure described above.

[0153] The composition of the present disclosure can be suitably used, for example, as a fluorinating agent.

[0154] <Fluorination method of the present disclosure> The present disclosure also relates to a fluorination method including a step of fluorinating an object using a composition containing fluoride ions obtained by the production method of the present disclosure. The fluorination method including a step of fluorinating an object using the composition of the present disclosure also constitutes the present disclosure. According to the fluorination method of the present disclosure, fluorination can be carried out using a composition obtained by a simple method, and also using a composition with low impurities such as wear particles from equipment.

[0155] The substance to be fluorinated may have a group that can be substituted with a fluorine atom. The substance is preferably a compound having at least one group that can nucleophilically react with a fluorine atom, and more preferably an organic compound having at least one group that can nucleophilically react with a fluorine atom.

[0156] Examples of the group capable of nucleophilically reacting with a fluorine atom include a chlorine atom, a bromine atom, an iodine atom, a hydrogen atom, a hydroxy group, and an organic group. The organic group preferably has 1 or more carbon atoms, more preferably 2 or more carbon atoms, and preferably 10 or less, more preferably 7 or less carbon atoms. The organic group may be an alkenyl group, an alkynyl group, an OSO2R 2 (R 2 is an organic group having 1 to 10 carbon atoms), a carboxy group, etc. The group capable of nucleophilically reacting 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 hydroxy group, more preferably at least one selected from the group consisting of a chlorine atom, a bromine atom, and a hydroxy 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.

[0157] The fluorination can be carried out by contacting the composition with the object. The method of contacting is not limited, and known methods can be used.

[0158] The amount of the composition used in the fluorination is preferably 1.0 equivalent or more, more preferably 1.3 equivalents or more, even more preferably 2.0 equivalents or more, and is preferably 10 equivalents or less, more preferably 5.0 equivalents or less, even more preferably 3.0 equivalents or less, relative to 1 equivalent of the group that can be substituted with a fluorine atom possessed by the target substance. In calculating the equivalent weight of the above composition, the molecular weight of the composition is calculated 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 organic base, and x:1 is the equivalent ratio of the two in the composition (fluorine-containing compound:organic base). Molecular weight of composition = xM1 + M2

[0159] The fluorination is preferably carried out in the presence of a solvent, such as water, an organic solvent, or a mixture thereof. Examples of the organic solvent 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, isopropanol, and ethylene glycol monoalkyl ether; 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, and mixtures thereof.

[0160] The fluorination temperature is preferably 5°C or higher, more preferably 10°C or higher, even more preferably 15°C or higher, and even more preferably 20°C or higher, and is 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.

[0161] The fluorination time is preferably 1 minute or more, more preferably 5 minutes or more, and even more preferably 10 minutes or more, and is 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.

[0162] It is also preferable to carry out the fluorination in a dry manner. It has been found that the fluorination reaction proceeds even in a dry manner when the composition obtained by the production method of the present disclosure is used. Carrying out the 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.

[0163] The fluorination is also preferably carried out by mechanochemically treating the composition and the object. When the fluorination is carried out by a dry method, it is particularly preferable to employ mechanochemical treatment. The conditions for the mechanochemical treatment of the composition and the object can be the same as those described in the manufacturing method of the present disclosure.

[0164] It is also preferable to carry out the step of obtaining the composition and the step of fluorination continuously. 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 step of fluorination after the step of obtaining the composition without isolating or purifying the product. It is also preferable to carry out the step of fluorination by mechanochemical treatment. Although the specific implementation method is not limited, it is preferable that, for example, after the step of obtaining the composition is completed, the object to be fluorinated is charged into the same reaction vessel without removing the contents of the reaction vessel, and the fluorination reaction is carried out.

[0165] By the above fluorination, a crude product containing a fluorinated target substance (a compound in which a group that can be substituted with a fluorine atom has been substituted with a fluorine atom) is obtained.

[0166] The fluorination method of the present disclosure also preferably includes a step of purifying the crude product obtained by fluorination to recover the fluorinated target substance. The purification method is not particularly limited, and any known method can be used.

[0167] The fluorination method of the present disclosure can be used to produce various compounds having fluorine atoms, and can be particularly suitably used to produce fluorine-containing organic compounds.

[0168] Although the embodiments have been described above, it will be understood that various changes in form and details can be made without departing from the spirit and scope of the claims. [Example]

[0169] The present disclosure will now be described in more detail with reference to examples, but the present disclosure is not limited to these examples.

[0170] In Examples 1 to 8, the physical properties were measured by the following methods. <Fluoride ions (F - ) and base content measurement It was measured by ion chromatography. After the reaction, the mixture was filtered using distilled water to remove the liquid, and the residue was diluted with distilled water. Measurements were then carried out using a Tosoh IC-8100ST equipped with a column (TSKgel (registered trademark) SuperIC-Anion HS) at an oven temperature of 40°C and a flow rate of 1.50 mL / min.

[0171] In Examples 1 to 8, the following materials (all solid at 25° C.) were used. Fluoropolymer A-1: ​​PVdF (VdF homopolymer, manufactured by BLD Pharmatech Ltd.), powder Fluoropolymer A-2: PTFE (TFE homopolymer, 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)

[0172] Example 1 A 10 mL stainless steel jar was charged with a stainless steel ball (10 mm), 0.5 eq. (equivalent) of fluororesin 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 fluororesin). The jar was closed and placed in a ball mill (Retsch Mixer Mill MM 400). Mechanochemical treatment using the ball mill was carried out at room temperature (25°C) and 30 Hz for 60 minutes. After completion, the jar was opened, washed with water, and concentrated in vacuo. The resulting composition (reaction mixture) was diluted with water and analyzed by ion chromatography. The resulting composition was 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 counter ion of the fluoride ion is K. The yield of KF is shown in Table 1. The yield was calculated assuming that the case in which all of the counter ions K in the base B-1 were converted to KF was 100%.

[0173] Example 2 A 10 mL stainless steel jar was charged with a stainless steel ball (10 mm), 5.0 eq. (equivalent) of fluororesin 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 using the ball mill was carried out at room temperature (25°C) and 30 Hz for 30 minutes. After completion, the jar was opened, washed with water, and concentrated in vacuo. The resulting composition (reaction mixture) was diluted with water and analyzed by ion chromatography. The resulting composition was solid (powder) at 25° C. and contained fluororesin A-1, base B-1, and 2.9 mass % of fluoride ions. The counter ion of the fluoride ion is K. The yield of KF is shown in Table 1.

[0174] Example 3 The mechanochemical treatment was carried out 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 solid (powder) at 25° C. and contained fluororesin A-1, <7.3 mass % of base B-1, and 7.7 mass % of fluoride ions. The counter ion of the fluoride ion is K. The yield of KF is shown in Table 1.

[0175] 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 changed to 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 (the internal temperature was estimated to be approximately 150°C) with a heat gun. The resulting composition was solid (powder) at 25° C. and contained fluororesin A-2, base B-1, and 4.2 mass % of fluoride ions. The counter ion of the fluoride ion is K. The yield of KF is shown in Table 1.

[0176] Example 5 The mechanochemical treatment was carried out in the same manner as in Example 4, except that 1.0 eq. of fluororesin A-2 was changed to 3.0 eq. of fluororesin A-3, the reaction time was changed to 180 minutes, and the outer 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 mass % of fluoride ions. The counter ion of the fluoride ion is K. The yield of KF is shown in Table 1.

[0177] Example 6 The mechanochemical treatment was carried out 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 was changed to B-2 (1.0 eq.). The resulting composition was 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 counter ion of the fluoride ion is K. The yield of KF is shown in Table 1.

[0178] Example 7 Except for changing the base to B-3, a mechanochemical treatment was carried out in the same manner as in Example 6. The obtained composition was a solid (powder) at 25°C and contained the fluororesin A-1, the base B-3, and 8.8 mass% of fluoride ions. The counter ion of the fluoride ion is K. The yield of KF is shown in Table 1.

[0179] Example 8 Except for changing the base to B-4, a mechanochemical treatment was carried out in the same manner as in Example 6. The obtained composition was a solid (powder) at 25°C and contained the fluororesin A-1, the base B-4, and 8.1 mass% of fluoride ions. The counter ion of the fluoride ion is Na. The yield of NaF is shown in Table 1.

[0180] [Table 1]

[0181] Example 9 Nitrogen gas was sealed into an oven-dried vial equipped with a magnetic stir bar. 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 mixture was stirred in the vial under a nitrogen gas atmosphere at room temperature (25°C) for 12 hours. The yield of the obtained p-toluoyl fluoride was determined using 4-fluoroanisole as an internal standard. 19 It was determined by F NMR to be 52%.

[0182] Example 10 To a glass reaction vessel equipped with a magnetic stir bar, the composition obtained in Example 3 (0.3 mmol, 1.5 eq.), the sulfonyl chloride (R-SOCl, 0.2 mmol, 1.0 eq.) shown in Table 2, distilled water (2.0 eq., 0.4 mmol), and acetone (0.2 M) were added as a solvent. After stirring the reaction mixture at room temperature for 30 minutes, the resulting suspension or crude product was filtered through a plug of silica eluted with EtOAc to remove insoluble by-products, and the solvent was removed by concentration under reduced pressure to obtain the corresponding sulfonyl fluoride (R-SOF). The yields of the resulting sulfonyl fluorides (Entry 9, 10, and 11) were calculated as follows: 19 The yields were calculated using F NMR with 4-fluoroanisole as the internal standard. All other yields are isolated yields.) are shown in Table 2.

[0183] [Table 2]

[0184] Example 11 Nitrogen gas was sealed into an oven-dried vial equipped with a magnetic stir bar. Next, the composition obtained in Example 2 (0.2 mmol, 1.5 eq.), dry ethyl acetate (1 mL), and the acyl chloride (R-COCl, 0.2 mmol, 1.0 eq.) shown in Table 3 were sequentially added. The mixture was stirred in a vial under a nitrogen gas atmosphere at room temperature (25°C) for 12 hours. Isolation and purification were carried out using silica gel column chromatography to obtain the corresponding acyl fluoride (R-COF). The yields of the obtained acyl fluorides (isolation yields) are shown in Table 3.

[0185] [Table 3]

[0186] Example 12 A glass reaction vessel was charged with the composition obtained in Example 3 (2.0 eq., 0.4 mmol), the bromide (R-Br, 0.2 mmol, 1.0 eq.) shown in Table 4, 18-crown-6-ether (1.0 eq.), HO (18 μL, 5.0 eq.), and anhydrous tBuOH (0.8 mL). After stirring at 100 °C for the time shown in Table 4, the resulting suspension was cooled to room temperature, filtered with EtOAc to remove insoluble by-products, and concentrated under reduced pressure to remove the solvent. Purification was carried out using silica gel column chromatography to obtain the corresponding fluoride (RF). The yields (isolation yields) of the resulting fluorides are shown in Table 4.

[0187] [Table 4]

[0188] Example 13 A 1.5 mL stainless steel jar was charged with a stainless steel ball (5 mm), the composition obtained in Example 3 (1.5 eq., 0.3 mmol), and the sulfonyl chloride (R-SOCl, 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 using the ball mill was carried out at room temperature (25 °C) and 30 Hz for 5 minutes. After completion, the jar was opened, washed with ethyl acetate, and concentrated in vacuo to obtain the corresponding sulfonyl fluoride (R-SOF). The yields of the obtained sulfonyl fluorides (Entry 1 is the yield measured by gas chromatography (GC) using mesitylene as an internal standard; the other entries are isolated yields) are shown in Table 5.

[0189] [Table 5]

[0190] Example 14 A 1.5 mL stainless steel jar was charged with a 5 mm stainless steel ball, 5.0 eq. of fluororesin 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 using the ball mill was carried out at room temperature (25°C) and 30 Hz for 60 minutes. After completion, the jar was opened, and the 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 using the ball mill was carried out at room temperature (25°C) and 30 Hz for 5 minutes. After completion, the jar was opened, washed with ethyl acetate, and concentrated in vacuo. The yield of the target sulfonyl fluoride (R-SO2F) was determined using hexafluorobenzene as an internal standard. 19 The results were measured by F NMR and are shown in Table 6.

[0191] [Table 6]

[0192] Example 15 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 12, except that the mixture was stirred at 100°C for 10 hours. The yield of the fluoride was 74%.

[0193] Example 16 Fluorination was carried out in the same manner as in Example 12, except that 0.5 eq. of fluororesin A-1, 1.0 eq. of base B-1, and sulfonyl chloride were changed to p-toluenesulfonyl chloride. The fluorination yield was 1%.

[0194] Example 17 Fluorination was carried out in the same manner as in Example 16, except that 2.0 eq. of fluororesin A-1 was used. The fluorination yield was 90%.

[0195] In Examples 18 to 25, the physical properties were measured by the following methods. <Fluoride ions (F - ) Content Measurement> Fluoride ions were quantified by NMR using a calibration curve prepared as described below.

[0196] KF calibration curve In a nitrogen atmosphere glove box, KF (spray-dried) was added to a 100 mL volumetric flask (made of polypropylene) containing 1.0 mL of CF3COOK solution (1.0 mol / L), and diluted to 100 mL with water to prepare four samples with different concentrations (0.010, 0.030, 0.090, and 0.27 mol / L). A portion of the 100 mL solution sample was taken and diluted with heavy water, 19 F NMR measurements were performed. This measurement was performed twice at each concentration. 19 A calibration curve was created based on the integral ratio of the F NMR measurement results. This calibration curve was used to quantify KF in each sample.

[0197] LiF calibration curve LiF was added to a 100 mL volumetric flask (made of polypropylene) containing 1.0 mL of CF3COOK solution (1.0 mol / L), and then diluted to 100 mL with water to prepare five samples with different concentrations (0.010, 0.020, 0.030, 0.040, and 0.050 mol / L). A portion of the 100 mL solution sample was taken and diluted with heavy water, and then 19 F NMR measurements were performed. This measurement was performed twice at each concentration. 19 A calibration curve was created based on the integral ratio of the F NMR measurement results. This calibration curve was used to quantify LiF in each sample.

[0198] NaF calibration curve NaF was added to a 100 mL volumetric flask (made of polypropylene) containing 1.0 mL of CF3COOK solution (1.0 mol / L), and diluted to 100 mL with water to prepare four samples with different concentrations (0.020, 0.030, 0.040, and 0.050 mol / L). A portion of the 100 mL solution sample was taken and diluted with heavy water, and then 19F NMR measurements were performed. This measurement was performed twice at each concentration. 19 A calibration curve was created based on the integral ratio of the F NMR measurement results. NaF in each sample was quantified using this calibration curve.

[0199] <Carbon content in carbon-based materials> The crude product obtained in each example was analyzed by CHN.

[0200] <Fluorine content in polyolefin> The crude product obtained in each example was analyzed by combustion ion chromatography.

[0201] <Amount of organic fluorine in the composition> The crude compositions obtained in each example were analyzed by combustion ion chromatography.

[0202] <Presence or absence of fluororesin in the composition> The composition was subjected to NMR analysis to determine whether or not fluororesin was present.

[0203] In Examples 18 to 25, the following materials were used. Fluoropolymer C-1: PTFE (TFE homopolymer, Kitamura Co., Ltd., KTL-2N) Fluoropolymer C-2: PVdF (VdF homopolymer, manufactured by BLD Pharmatech Ltd.), powder Reducing agent D-1: K (single) (reduction potential: -2.93 V) Reducing agent D-2: Li (single element) (reduction potential: -3.04 V) Reducing agent D-3: Na (single element) (reduction potential: -2.71 V) Reducing agent D-4: Zn (single element) (reduction potential: -0.76 V) Reducing agent D-5: Mg (single element) (reduction potential: -2.36 V) Proton source E-1: Ethylenediamine Proton source E-2: t-butyl alcohol Proton Source E-3: 1-Adamantanol

[0204] Example 18 In a glove box, a 10 mL stainless steel jar was charged with a stainless steel ball (10 mm), 1.0 eq. (equivalent) of fluororesin C-1 (100 mg, 1 mmol, calculated based on the molecular weight of the constituent monomer TFE (100.02)), and 4.4 eq. of reducing agent D-1 (172.0 mg, 4.4 mmol). The jar was closed and placed in a ball mill (Retsch Mixer Mill MM 400). Mechanochemical treatment using the ball mill was carried out at room temperature (25 °C) and 30 Hz for 1 hour. Upon completion, the jar was opened, quenched with methanol and water, and the jar was washed with diethyl ether. The heterogeneous solution was filtered with water and diethyl ether. The filtrate was concentrated in vacuo to remove the methanol, and diethyl ether was added to the solution, which was then extracted three times with water. The aqueous layer was concentrated. The sample was diluted with water and 1.0 mL of CF3COOK solution (1.0 mol / L) was added to a 100 mL volumetric flask (made of polypropylene) to prepare a 100 mL sample. The KF yield was determined by NMR measurement. The results are shown in Table 7. The composition (reaction mixture) obtained by the mechanochemical treatment was a solid (powder) at 25°C. NMR measurements of the solid, organic layer, and aqueous layer obtained by filtration and extraction revealed that it contained 26% by mass of fluoride ions, 53% by mass of K as a counter ion, and a carbon-based substance. The carbon-based substance was amorphous carbon with a carbon content of 67% by mass. The amount of organic fluorine in the carbon-based substance was 0.16% by mass. NMR did not confirm the presence of fluororesin C-1.

[0205] Example 19 The same procedure as in Example 18 was carried out except that 8.8 eq. (equivalents) of proton source E-1 was further added as a reactant and the reaction time was changed to 10 minutes. The results are shown in Table 7.

[0206] Example 20 The same procedure as in Example 18 was repeated, except that fluororesin C-2 (256 mg, 4.0 mmol, calculated based on the molecular weight of the constituent monomer VdF (64.03)) was used instead of fluororesin C-1, and the amount of reducing agent D-1 was changed to 2.2 eq. (equivalents). The results are shown in Table 7.

[0207] Example 21 The same procedure as in Example 18 was carried out except that 4.4 eq. (equivalents) of reducing agent D-3 was used instead of reducing agent D-1. The results are shown in Table 7.

[0208] Example 22 In a glovebox, a 10 mL stainless steel jar was charged with a stainless steel ball (10 mm), 1.0 eq. (equivalent) of fluororesin C-1 (100 mg, 1 mmol, calculated based on the molecular weight of the constituent monomer TFE (100.02)), 8.0 eq. of reducing agent D-2 (55 mg, 8 mmol), and 40.0 eq. of proton source E-1 (2.4 g, 40 mmol). The jar was then closed and placed in a ball mill (Retsch Mixer Mill MM 400). Mechanochemical treatment using the ball mill was carried out at room temperature (25 °C) at 30 Hz for 1 hour. Upon completion, the jar was opened, quenched with water, ultrasonically stirred for 1 minute, and stirred with a stirrer for 1 hour, and then filtered. The solid was washed with water and diethyl ether. The filtrate was extracted three times with water, and the aqueous layer was concentrated in vacuo. The yield of LiF was determined by NMR analysis. The results are shown in Table 7. The composition (reaction mixture) obtained by mechanochemical treatment was in a slurry state at 25°C. NMR measurements of the solid, organic layer, and aqueous layer obtained by filtration and extraction showed that it contained 3% by mass of fluoride ions, Li as a counter ion, and polyethylene. The carbon content of the residue after amine removal was 76% by mass. The fluorine content of the polyethylene was 1.7% by mass.

[0209] Example 23 The same procedure as in Example 22 was carried out except that the amount of proton source E-1 was changed to 16.0 eq. and an additional 8.0 eq. of proton source E-3 was added. The results are shown in Table 7.

[0210] Example 24 The same procedure as in Example 18 was carried out except that reducing agent D-4 was used instead of reducing agent D-1. The results are shown in Table 7.

[0211] Example 25 The same procedure as in Example 18 was carried out except that reducing agent D-5 was used instead of reducing agent D-1. The results are shown in Table 7.

[0212] [Table 7]

[0213] Example 26 The same procedure as in Example 18 was carried out, except that the fluororesin C-1 was replaced with activated carbon (1.05 g) on ​​which a low-molecular-weight fluorine compound had been adsorbed in advance, and 1.1 eq. of reducing agent D-1 was added relative to F. NMR analysis of the obtained composition confirmed that KF was produced in a yield of 51%.

[0214] Example 27 Fluorine resin C-1 is mixed with C 12 F 25 The procedure of Example 18 was repeated, except that the amount of reducing agent D-1 was changed to 149 mg of F, and 1.1 eq. of reducing agent D-1 was added relative to F. NMR analysis of the resulting composition confirmed that KF was produced in a yield of 96%.

[0215] Example 28 An experiment was carried out in the same manner as in Example 18, except that the fluororesin C-1 was changed to PFA. NMR analysis of the obtained composition confirmed that KF was produced in a yield of 6%.

[0216] Example 29 A 10 mL stainless steel jar was charged with a stainless steel ball (10 mm), 1.0 eq. of fluororesin C-1 (100 mg, 1 mmol), and 4.4 eq. of reducing agent D-1 (172.0 mg, 4.4 mmol). The jar was closed and placed in a ball mill (Retsch Mixer Mill MM 400). Mechanochemical treatment using the ball mill was carried out at room temperature (25 °C) and 30 Hz for 60 minutes. Upon completion, the jar was opened and p-toluenesulfonyl chloride (R-SO2Cl, 2 mmol, 1.0 eq.) was added to the mixture. The jar was closed and mechanochemical treatment using the ball mill was carried out at room temperature (25 °C) and 30 Hz for 5 minutes. Upon completion, the jar was opened, washed with ethyl acetate, and concentrated in vacuo. The yield of the target sulfonyl fluoride (R-SO2F) was determined using hexafluorobenzene as an internal standard. 19 The yield was 18% as determined by F NMR.

[0217] Example 30 The same procedure as in Example 29 was repeated, except that the equivalents of the fluororesin C-1 were changed to 1.1 eq. (110 mg, 1.1 mmol) and the equivalents of the reducing agent D-1 were changed to 4.0 eq. (156.3 mg, 4.0 mmol). The yield of the target sulfonyl fluoride was 73%.

[0218] Example 31 The composition obtained in Example 18 (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 placed in a glass reaction vessel. The procedure was the same as in Example 12, except that the mixture was stirred at 100°C for 10 hours. The fluorination yield was 69%.

[0219] Example 32 A composition (41 wt% KF, 1.5 eq., 0.3 mmol) obtained in the same manner as in Example 22, except that 8.0 eq. of reducing agent D-1 was used, was added to p-toluenesulfonyl chloride (1.0 eq., 2.0 mmol), water (7.2 μL, 2.0 eq.), and acetone (0.8 mL). The same procedure as in Example 12 was carried out, except that the mixture was stirred at room temperature for 30 minutes. The fluorination yield was 25%.

[0220] Experimental Example 33 Commercially available KF (298 mg) was weighed in a glove box and stored in the atmosphere for 24 hours. The mass (X mg) was measured, and the mass increase rate was calculated using the following formula, which was 20%. Growth rate (%) = (X-298) / 298 x 100 The mass increase rate of the composition obtained in Example 1 was similarly determined and was found to be 12%.

Claims

1. A method for producing a composition, comprising a step of mechanochemically treating a fluorine-containing compound with at least one selected from the group consisting of an organic base, a reducing agent, and a proton source to react the fluorine-containing compound, thereby obtaining a composition containing fluoride ions.

2. 2. The method according to claim 1, wherein the organic base has a pKa of 8 to 40.

3. The organic base is selected from alkali metals, alkaline earth metals, and NR １ ４ (R １ and may be the same or different, and contain at least one selected from the group consisting of H or an organic group having 1 to 10 carbon atoms.

4. The organic base is R １０ OM (in the formula, R １０ is an organic group having 1 to 10 carbon atoms, M is a metal or NR １ ４ (R １ and may be the same or different and represent H or an organic group having 1 to 10 carbon atoms.

5. 3. The method according to claim 1, wherein the organic base is at least one selected from the group consisting of sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide, sodium t-butoxide, and potassium t-butoxide.

6. 3. The process according to claim 1, wherein the amount of the organic base used is 0.10 to 3 equivalents per equivalent of the fluorine-containing compound.

7. 3. The method according to claim 1, wherein the reducing agent has a standard electrode potential of −0.44 V or less.

8. 3. The method according to claim 1, wherein the reducing agent is at least one selected from the group consisting of Zn, Fe, Al, alkali metals, and alkaline earth metals.

9. 3. The method according to claim 1, wherein the reducing agent is at least one selected from the group consisting of alkali metals and alkaline earth metals.

10. 3. The method according to claim 1, wherein the reducing agent is at least one selected from the group consisting of Li, Na, K, Mg, and Ca.

11. 3. The method according to claim 1, wherein the reducing agent is at least one selected from the group consisting of K and Ca.

12. 3. The method according to claim 1, wherein the amount of the reducing agent used is 0.7 to 20 equivalents per equivalent of the fluorine-containing compound.

13. 3. The method according to claim 1, wherein the proton source is at least one selected from the group consisting of amines and alcohols.

14. 3. The method according to claim 1, wherein the proton source is at least one selected from the group consisting of ethylenediamine, methanol, ethanol, t-butyl alcohol, and 1-adamantanol.

15. 3. The method according to claim 1, wherein the proton source is a primary amine.

16. 3. The method according to claim 1, wherein the proton source is ethylenediamine.

17. 3. The method according to claim 1, wherein the amount of the proton source used is 8 to 50 equivalents per equivalent of the fluorine-containing compound.

18. 3. The method according to claim 1, wherein the fluorine-containing compound and the organic base are subjected to a mechanochemical treatment.

19. 3. The method according to claim 1, wherein the fluorine-containing compound and the reducing agent are subjected to a mechanochemical treatment.

20. 3. The method according to claim 1, wherein the fluorine-containing compound, the reducing agent, and the proton source are subjected to a mechanochemical treatment.

21. 3. The method according to claim 1, wherein the fluorine-containing compound is solid at 25°C.

22. 3. The method according to claim 1, wherein the fluorine-containing compound is a fluorine-containing polymer.

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

24. 3. The method according to claim 1, wherein the fluorine-containing compound is at least one selected from the group consisting of perfluororesins and polydifluoroethylenes.

25. 3. The method according to claim 1, wherein the fluorine-containing compound is at least one selected from the group consisting of polytetrafluoroethylene and polydifluoroethylene.

26. 3. The method according to claim 1, wherein the fluorine-containing compound is at least one selected from the group consisting of polytetrafluoroethylene, polyvinylidene fluoride, and polychlorotrifluoroethylene.

27. A fluorination method comprising the step of fluorinating an object using a composition containing fluoride ions obtained by the method of claim 1 or 2.

28. 28. The fluorination process according to claim 27, wherein the fluorination is carried out dry.

29. 28. The fluorination method according to claim 27, wherein the fluorination is carried out by mechanochemically treating the composition and the object.

30. 28. The fluorination process according to claim 27, wherein the step of obtaining the composition and the step of fluorinating are carried out consecutively.

31. 28. The method for fluorination according to claim 27, wherein the amount of the composition used is 1.0 to 3.0 equivalents per equivalent of the group that can be substituted with a fluorine atom that the object has.

32. 28. The fluorination method according to claim 27, wherein the target substance is an organic compound having at least one atom selected from the group consisting of a chlorine atom and a bromine atom.

33. A composition comprising fluoride ions and a carbon-based substance and / or a polyolefin having a fluorine content of 10% by mass or less.

34. 34. The composition of claim 33, wherein the carbon-based material is amorphous carbon.

35. 35. The composition of claim 33 or 34, wherein the polyolefin is polyethylene.

36. The composition according to claim 33 or 34, wherein the content of the fluoride ions is 1 to 30 mass%.

37. The composition according to claim 33 or 34, which is substantially free of fluororesin.

38. 35. The composition of claim 33 or 34, which is a fluorinating agent.

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