Composition production method, fluorination method, and composition

Abstract

Provided are: 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. 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 type of substance selected from the group consisting of organic bases, reducing agents, and proton sources.

Description

Method for producing composition, fluorination method, and composition

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

[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).

[0003] Japanese Patent Application Laid-Open No. 2001-253969

[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.

[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 pKa of the organic base is 8 to 40.

[0007] The present disclosure (3) is directed to a method for preparing a hydroxybenzoate comprising the step of: １ ４ (R １ may be the same or different, and may be H or an organic group having 1 to 10 carbon atoms).

[0008] The present disclosure (4) is directed to a method in which 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 may be the same or different and represent H or an organic group having 1 to 10 carbon atoms.) The present invention relates to a method for producing an arbitrary combination of a compound represented by the formula (1) with any of the compounds of the present disclosure (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 manufacturing method of 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 any combination 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), wherein 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 any 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 mechanochemical treatment.

[0024] The present disclosure (20) is a method for producing any combination 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 any 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 any 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 (23), 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 any combination of the production method of 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 of 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), wherein 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), 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.

[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 of any combination with any of the present disclosures (33) to (35), in which the content of fluoride ions is 1 to 30 mass%.

[0041] The present disclosure (37) is a composition that is an optional combination with any of the present disclosures (33) to (36), and that is substantially free of 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.

[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.

[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 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.

[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, without requiring high energy consumption. 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 may be used in combination. As described below, 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 are collectively referred to as the "production method of the present disclosure." Furthermore, the compositions of the present disclosure described below can be produced by production methods (2-1) and (2-2) of the present disclosure.

[0048] <Production Method (1) of the Present Disclosure> In Production Method (1) of the present disclosure, a fluorine-containing compound and an organic base are subjected to mechanochemical treatment. The fluorine-containing compound used in the production method of the present disclosure may be a compound having a fluorine atom, but may also 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. Furthermore, the fluorine-containing compound is preferably a solid at 25°C, in order to facilitate mechanochemical treatment.

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

[0050] The fluoropolymer preferably contains polymerization units based on at least one monomer selected from the group consisting of tetrafluoroethylene [TFE], difluoroethylene, chlorotrifluoroethylene [CTFE], hexafluoropropylene [HFP], perfluoro(alkyl vinyl ether) [PAVE], trifluoroethylene, and monofluoroethylene. Examples of the 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, even more preferably contains polymerization units based on at least one monomer selected from the group consisting of TFE, VdF, and CTFE, even more preferably contains polymerization units based on at least one monomer selected from the group consisting of TFE and VdF, and particularly preferably contains polymerization units based on VdF.

[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, Et / CTF Examples of the perfluoroalkyl allyl ether include CF3 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, TFE / perfluoroalkyl allyl ether copolymer, and the like, and these can be used alone or in combination. The perfluoroalkyl allyl ether is CF3 ２ =CFCF ２ -O-Rf １ (Rf １ is 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): CH ２ = CFRf ２ (1) (wherein, Rf ２ represents a linear or branched fluoroalkyl group having 1 to 12 carbon atoms)

[0055] As the fluorine-containing polymer, at least one selected from the group consisting of fluororesin and fluororubber is preferred, at least one selected from the group consisting of PTFE, FEP, PFA, PVdF, PCTFE and fluororubber is more preferred, at least one selected from the group consisting of PTFE, PVdF and PCTFE is even more preferred, at least one selected from the group consisting of PTFE and PVdF is even more preferred, PVdF is particularly preferred.In addition, as the fluorine-containing polymer, perhalogen resin is also preferred, at least one selected from the group consisting of perfluororesin and PCTFE is more preferred, at least one selected from the group consisting of PTFE, PFA, FEP and PCTFE is even more preferred, at least one selected from the group consisting of PTFE, PFA and FEP is even more preferred.In addition, as the fluorine-containing polymer, at least one selected from the group consisting of perfluororesin and polydifluoroethylene is also preferred, at least one selected from the group consisting of PTFE and polydifluoroethylene is more preferred.

[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 a compound represented by the following general formula (I): Y—(CF ２ ) ｘ１ - (CH ２ )ｙ１ -A (I) (wherein Y represents H or F, x1 represents an integer of 4 or more, and y1 represents an integer of 0 to 3. A is -CF(CF ３ ) ２ O.M. Ｉ , -PO(OM Ｉ ) ２ , -SO ３ M Ｉ or -COOM Ｉ indicates M Ｉ is H, NH ４ , Li, Na, Mg, Al, K or Ca), and a compound (I) represented by the following general formula (II): F—(CF ２ ) Ｘ２ O(CFXCF ２ O) ｙ２ -CFX-A (II) (wherein x2 represents an integer of 1 or more, y2 represents an integer of 0 to 10, and X represents F or CF ３ A represents -SO ３ M ＩＩ or -COOM ＩＩ indicates M ＩＩ is H, NH ４ , Li, Na, Mg, Al, K or Ca.

[0057] Examples of the compound (I) include fluorocarboxylic acids and their salts, preferably perfluorocarboxylic acids and their salts, such as perfluorooctanoic acid and its salts (collectively referred to as "PFOA"), perfluorohexanoic acid and its salts, and perfluorobutanoic acid and its salts. Examples of salts include ammonium salts and sodium salts, with ammonium salts being preferred, such as ammonium perfluorooctanoic acid (particularly referred to as "APFO"). Examples of the compound (I) also include fluorosulfonic acids and their salts, preferably perfluorosulfonic acids and their salts, such as perfluorooctanesulfonic acid and its salts (collectively referred to as "PFOS"). Examples of salts include ammonium salts and sodium salts. Examples of the compound (II) include perfluoroethercarboxylic acids and their salts, 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 obtained by adsorbing the fluorine-containing low molecular weight compound 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 fluorine-containing compound and other components may be subjected to mechanochemical treatment. The other components may be used within a range that does not impair the effects of the present disclosure. Examples of the other components include general fillers, polymers, and the adsorbents described above.

[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 polyamino bismaleimide; 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 polymer may be a non-fluorine-containing polymer.

[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 melting point or higher. 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] In order to facilitate mechanochemical treatment using a general-purpose apparatus, 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, even more preferably 12 or more, and even more preferably 15 or more. The pKa is measured 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) or alkaline earth metals (Group 2), and specific examples include Na, K, Li, and Ca. Of these, alkali metals are preferred, with Na and K being more preferred, and K being even more preferred. NR １ ４ is ammonium (unsubstituted or substituted ammonium), and the four R １ may be the same or different. 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 base includes alkali metals, alkaline earth metals, and NR １４ (R １ may be the same or different, and may contain at least one selected from the group consisting of H or an organic group having 1 to 10 carbon atoms), 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, still 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. ) compounds represented by the formula (R), metal acetates, cyclic amines, polyamines, etc. 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 is preferably an alkyl group having a carbon number within the above range, more preferably a t-butyl group. １ ４ Examples of M 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 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 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 production method (1) of the present disclosure, the mechanochemical treatment can be carried out with a relatively small amount of organic base. A small amount of organic base has the advantage of facilitating purification and reducing the impact on the fluorination yield. When the fluorine-containing compound is a fluoropolymer, the equivalent is calculated based on the monomers constituting the fluoropolymer.

[0071] Mechanochemical treatment is a treatment 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, shaking, etc., to activate the reactant and impart structural change, phase transition, reactivity, adsorptivity, catalytic activity, etc. The method of mechanochemical treatment is not particularly limited, and examples include a compression 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 that can apply mechanical energy by the above-mentioned method, and known pulverizers and mixers can be used. For example, pulverizers such as a ball mill, rod mill, jet mill, vibration mill, SAG mill, etc.; attritors such as a rotary stone mill, crusher, etc.; (horizontal axis rotation) container rotation type mixers such as a horizontal cylindrical type, V type, double cone type, square cube type, S type, and continuous V type; (baffle blade equipped) container rotation type mixers such as a horizontal cylindrical type, V type, double cone type, and ball mill type; (rotation vibration) container rotation type mixers such as a rocking type and cross rotary type; (horizontal axis) container rotation type mixers such as a ribbon type, paddle type, single shaft rotor type, and bug 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 type; (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; and kneaders such as twin-screw kneaders, single-screw kneaders, mixers, roll mills, etc.

[0073] The apparatus for carrying out the mechanochemical treatment is preferably an apparatus using balls, and more preferably a ball mill (excluding planetary ball mills).

[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 imparting high energy, it also generates a large amount of wear debris from the device. 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 the 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, which is also used in the above-mentioned Patent Document 1. The inclusion of wear debris may interfere with the use of the composition after the reaction. When the composition after the reaction is to be used for applications such as fluorination, it is preferable that it does not contain impurities. The production method of the present disclosure can react a fluorine-containing compound under conditions that are unlikely to generate wear powder derived from the equipment, so the resulting composition can be used as a fluorinating agent, etc. In addition, a method using a general-purpose equipment such as a ball mill rather than 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, and 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 performed using a ball mill (excluding planetary ball mills), the shaking conditions can be determined depending on the apparatus and ball used. For example, when treating using a jar of approximately 1 to 20 mL and one stainless steel ball with a diameter of approximately 1 to 15 mm, shaking can be performed at a speed 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, and even more preferably 1500 rpm or less. It can also be performed at a frequency 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, and 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 sometimes promote 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 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, 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, 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 counter ions together with fluoride ions. The counter ions 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 ４ 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 low.

[0090] The composition obtained by the production method (1) of the present disclosure preferably does not substantially contain 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 even 0.0001% by mass. The content of organic fluorine in the fluorinating agent is measured by combustion ion chromatography. Incidentally, organic fluorine means 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 can be prevented in the subsequent fluorination step, 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 fluorine-containing compound is defluorinated (by mechanochemical treatment). The compound may have a structure in which at least some of the fluorine atoms in the fluorine-containing compound are defluorinated. The compound may have a structure in which at least some of the fluorine atoms in the fluorine-containing compound are defluorinated, such as a structure derived from the organic base, for example, R １０ O-(R １０ is the same as above). 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 is preferably a powder, in terms 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 is 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. Compositions with a maximum particle size within the above range are free from agglomerates and are easy to handle.

[0096] <Production Method (2-1) of the Present Disclosure> In production method (2-1) of the present disclosure, a fluorine-containing compound and a reducing agent are subjected to mechanochemical treatment. This allows a composition containing fluoride ions to be obtained under relatively mild conditions. Note that 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 fluorine-containing compound, but in terms 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 Revised 6th Edition Chemistry Handbook.

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

[0100] Examples of the alkali metal include Li, Na, and K, with Li and K being preferred. Examples of the alkali earth metal include Mg, Ca, and Sr, with Mg and Ca being preferred, and 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. At least one selected from the group consisting of K and Ca is also preferred. The reducing agent is also 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 reducing agent used in the production method (2-1) of the present disclosure is preferably 0.01 equivalents or more relative to 1 equivalent (molar equivalent) of the fluorine-containing compound, more preferably 0.05 equivalents or more, even more preferably 0.10 equivalents or more, even more preferably 0.50 equivalents or more, even more preferably 0.70 equivalents or more, particularly preferably 1 equivalent or more, and 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, particularly preferably 1.5 equivalents or less. In the production method (2-1) of the present disclosure, mechanochemical treatment can be performed with a relatively small amount of reducing agent. When the reducing agent is used in a small amount, there is an advantage that decomposition of the substrate in the fluorination step can be prevented.

[0103] The mechanochemical treatment in the production method (2-1) 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.

[0104] The temperature of the mechanochemical treatment in the production 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 performed at a relatively low temperature.

[0105] When the mechanochemical treatment in the production method (2-1) of the present disclosure is performed using a ball mill (excluding planetary ball mills), the shaking conditions can be determined depending on the apparatus and ball used. For example, when treating using a jar of approximately 1 to 20 mL and one stainless steel ball with a diameter of approximately 1 to 15 mm, shaking can be performed 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, and even more preferably 1500 rpm or less. It can also 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, and 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 manufacturing 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 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, since the reaction proceeds sufficiently in the production method (2-1) of the present disclosure even without a solvent, it is preferable not to use a solvent. Note that, 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 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.

[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 production method (2-2) of the present disclosure, a fluorine-containing compound, a reducing agent, and a proton source are subjected to mechanochemical treatment, thereby making it possible to obtain a composition containing fluoride ions 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] As the reducing agent in the production method (2-2) of the present disclosure, the same reducing agent as in the production method (2-1) of the present disclosure can be used, and the preferred forms are also similar, but it is also preferable that the reducing agent is at least one selected from the group consisting of K, Li, and Ca, it is also preferable that the reducing agent is at least one selected from the group consisting of K and Li, and it is also preferable that the reducing agent is Li.

[0116] The amount of 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, more preferably 0.10 equivalents or more, even more preferably 0.50 equivalents or more, even more preferably 0.70 equivalents or more, particularly preferably 1 equivalent or more, and 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, particularly preferably 2 equivalents or less. In the production method (2-2) of the present disclosure, mechanochemical treatment can be performed with a relatively small amount of reducing agent. When the reducing agent is used in a small amount, there is an advantage that decomposition of the substrate can be prevented 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] Examples of the proton source include amines and alcohols, and one or more of these may 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. Among the amines, diamines having a primary amino group are preferred, with ethylenediamine being 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. Among these, at least one selected from the group consisting of ethylenediamine, t-butyl alcohol, and 1-adamantanol is preferred. Among these, at least one selected from the group consisting of ethylenediamine, t-butyl alcohol, and 1-adamantanol is preferred.

[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 production 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 performed at a relatively low temperature.

[0122] When the mechanochemical treatment in the 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 treating using a jar of approximately 1 to 20 mL and one stainless steel ball with a diameter of approximately 1 to 15 mm, 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, and even more preferably 1500 rpm or less. It can also be carried out 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, and 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 manufacturing 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 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, since the reaction proceeds sufficiently in the production method (2-2) of the present disclosure even without a solvent, it is preferable not to use a solvent. Note that, 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] Examples of 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 carrying out a 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, thereby providing, for example, the composition (2) of the present disclosure described below.

[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 for decomposing (defluorinating) fluorine-containing compounds. The production method of the present disclosure can also be used to produce a compound having fluoride ions. In this case, the composition obtained by the production method of the present disclosure may be purified to recover the compound having fluoride ions. 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 is, or the 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 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 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, or 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 determined as a percentage of the total amount excluding the proton source.

[0134] The composition of the present disclosure typically contains a counterion along with the fluoride ion. The counterion 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 counterion is also preferably at least one selected from the group consisting of alkali metals and alkaline earth metals, 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, at least one selected from the group consisting of Li, K, and Ca is even more preferred, with Li being particularly preferred. These may be contained 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, at least one selected from the group consisting of lithium fluoride, sodium fluoride, potassium fluoride, and calcium fluoride is preferred, more preferably at least one selected from the group consisting of lithium fluoride, sodium fluoride, and potassium fluoride, and particularly preferably potassium fluoride. 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, and lithium fluoride is 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. A 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. A 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 relative to 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 fluororesin). The carbon-based substance may be amorphous carbon.

[0142] The content of the carbon-based substance 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 a repeating unit based on an olefin. Examples of the olefin include ethylene and propylene. The repeating unit may be one type or two or more types. The olefin is preferably ethylene or a combination of ethylene and propylene, more preferably ethylene. The polyolefin is preferably at least one selected from the group consisting of polyethylene and ethylene-propylene copolymer, 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 actually obtained by polymerizing an olefin. The polyolefin may further have a structure other than a 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 fluorine content 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, and may be 50% by mass or less, 40% by mass or less, or 30% by mass or less, based on the total amount excluding the proton source.

[0147] Preferably, the composition of the present disclosure is 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 even 0.0001% by mass. When the composition contains a proton source, the content is determined 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, "fluororesin" refers to a resin having a fluorine content of more than 10% by mass. The method for measuring the fluorine content in a polymer is as described above. Furthermore, "organic fluorine" means fluorine bonded to carbon. Even when no fluororesin is detected by NMR analysis of the composition, it can be said that the composition is substantially free of fluororesin.

[0148] It is also preferred that the composition of the present disclosure is substantially free of fluorine-containing polymer. "Substantially free of fluorine-containing polymer" 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 proportion relative to 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. Even when no fluorine-containing polymer is confirmed by NMR analysis of the composition, it can be said that the composition is substantially free of 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 described above. The fluorination method including a step of fluorinating an object using the composition of the present disclosure described above also constitutes the present disclosure. According to the fluorination method of the present disclosure, fluorination can be performed using a composition obtained by a simple method. Furthermore, fluorination can also be performed using a composition with low impurities such as wear powder 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 number of carbon atoms in the organic group is preferably 1 or more, more preferably 2 or more, and is preferably 10 or less, more preferably 7 or less. Examples of the organic group include an alkenyl group, an alkynyl group, an OSO group, and the like. ２ R ２ (R ２is 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 contacting method is not limited, and known methods can be used.

[0158] In the fluorination, the amount of the composition used is preferably 1.0 equivalent or more, more preferably 1.3 equivalents or more, even more preferably 2.0 equivalents or more, and preferably 10 equivalents or less, more preferably 5.0 equivalents or less, 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 of the 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. Examples of the solvent include 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 when the composition obtained by the production method of the present disclosure is used, the fluorination reaction proceeds even in a dry manner. 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] It is also preferable that the fluorination is 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, for example, it is preferable that 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] The fluorination yields 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).

[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.

[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. －Measurement of the content of methyl methacrylate and base> Measurement was performed 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. Measurement was performed using an IC-8100ST manufactured by Tosoh Corporation 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: Fluororesin A-1: ​​PVdF (VdF homopolymer, manufactured by BLD Pharmatech Ltd.), powder Fluororesin A-2: PTFE (TFE homopolymer, manufactured by Kitamura Co., Ltd., KTL-2N) Fluororesin A-3: PCTFE (CTFE homopolymer, manufactured by Sigma-Aldrich), powder Base B-1: tBuOK (organic base, pKa = 17) Base B-2: KOMe (organic base, pKa = 16) Base B-3: KOEt (organic base, pKa = 17) Base B-4: tBuONa (organic base, pKa = 17)

[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 (64.03) of the constituent monomer VdF), 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 for 60 minutes at room temperature (25°C) and 30 Hz. Upon 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 a solid (powder) at 25°C and contained fluororesin A-1, <59 mass% of base B-1, and 1.8 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 of 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 (1,280 mg, 20 mmol, calculated based on the molecular weight (64.03) of the constituent monomer VdF), 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 for 30 minutes at room temperature (25°C) and 30 Hz. Upon 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 a solid (powder) at 25°C and contained fluororesin A-1, base B-1, and 2.9% by mass of fluoride ions. The counter ion for the fluoride ions was K. The yield of KF is shown in Table 1.

[0174] Example 3 A 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 obtained composition was a 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 ions was K. The yield of KF is shown in Table 1.

[0175] Example 4 A 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 (1,200 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 (internal temperature estimated to be approximately 150°C) with a heat gun. The obtained composition was a 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 ions was K. The yield of KF is shown in Table 1.

[0176] Example 5 A 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 (the internal temperature was estimated to be about 100°C) with a heat gun. The obtained composition was a solid (powder) at 25°C and contained fluororesin A-3, base B-1, and 2.0 mass% fluoride ions. The counter ion of the fluoride ions was K. The yield of KF is shown in Table 1.

[0177] Example 6 A 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 obtained composition was a solid (powder) at 25°C and contained fluororesin A-1, <1.7 mass% of base B-2, and 9.1 mass% of fluoride ions. The counter ion of the fluoride ions was K. The yield of KF is shown in Table 1.

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

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

[0180]

[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 to be 52% by F NMR.

[0182] Example 10 In a glass reaction vessel equipped with a magnetic stir bar, the composition obtained in Example 3 (0.3 mmol, 1.5 eq.), sulfonyl chloride (R—SO ) shown in Table 2, and ２ Cl, 0.2 mmol, 1.0 eq.), distilled water (2.0 eq., 0.4 mmol), and acetone (0.2 M) as solvent were added. After stirring the reaction 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 give the corresponding sulfonyl fluoride (R-SO ２ The yields of the obtained sulfonyl fluorides (Entries 9, 10 and 11) were １９ The yields were calculated using F NMR with 4-fluoroanisole as an internal standard. The remaining yields are isolated yields.) are shown in Table 2.

[0183]

[0184] Example 11 Nitrogen gas was sealed in 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 the 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 yield (isolation yield) of the obtained acyl fluoride is shown in Table 3.

[0185]

[0186] Example 12 In a glass reaction vessel, the composition obtained in Example 3 (2.0 eq., 0.4 mmol), a bromide (R—Br, 0.2 mmol, 1.0 eq.) shown in Table 4, 18-crown-6-ether (1.0 eq.), H ２ 0 (18 μL, 5.0 eq.) and anhydrous tBuOH (0.8 mL) were added. 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. Isolation and purification were carried out using silica gel column chromatography to obtain the corresponding fluoride (R-F). The yields of the obtained fluorides (isolation yields) are shown in Table 4.

[0187]

[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 a sulfonyl chloride (R—SO ) shown in Table 5. ２ Cl, 0.2 mmol, 1.0 eq.) was added. The jar was closed and placed in a ball mill (Retsch Mixer Mill MM 400). Mechanochemical treatment using the ball mill was carried out for 5 minutes at room temperature (25°C) at 30 Hz. After completion, the jar was opened, washed with ethyl acetate, and concentrated in vacuo to give the corresponding sulfonyl fluoride (R-SO ２ The yields of the obtained sulfonyl fluorides (Entry 1 is the yield measured by gas chromatography (GC) using mesitylene as an internal standard; the others are isolated yields) are shown in Table 5.

[0189]

[0190] Example 14 A 1.5 mL stainless steel jar was charged with a stainless steel ball (5 mm), 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-SO ) shown in Table 6 was added to the mixture. ２Cl, 0.2 mmol, 1.0 eq.) was added. The jar was closed, and mechanochemical treatment was carried out using a ball mill at room temperature (25°C) at 30 Hz for 5 minutes. After completion, the jar was opened, washed with ethyl acetate, and concentrated in vacuo. The resulting target sulfonyl fluoride (R-SO ２ The yield of F) was calculated using hexafluorobenzene as an internal standard. １９ The results are shown in Table 6.

[0191]

[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 placed in 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 instead. The fluorination yield was 90%.

[0195] In Examples 18 to 25, the physical properties were measured by the following methods. － Measurement of fluoride ion content> A calibration curve was prepared as described below, and the fluoride ion content was quantified by NMR.

[0196] ・KF calibration curve KF (spray dried) in a nitrogen atmosphere glove box, ３ A 1.0 mL portion of the COOK solution (1.0 mol / L) was added to a 100 mL volumetric flask (made of polypropylene) 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, and then１９ F NMR measurements were performed. This measurement was performed twice for each concentration. １９ A calibration curve was created based on the integral ratio from the F NMR measurement results. Using this calibration curve, KF in each sample was quantified.

[0197] LiF calibration curve LiF, CF ３ 1.0 mL of COOK solution (1.0 mol / L) was added to a 100 mL volumetric flask (made of polypropylene) and diluted to 100 mL with water to prepare five samples with different concentrations (0.010, 0.020, 0.030, 0.040, 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 for each concentration. １９ A calibration curve was created based on the integral ratio from the F NMR measurement results. Using this calibration curve, the LiF in each sample was quantified.

[0198] ・NaF calibration curve NaF, CF ３ A 1.0 mL portion of the COOK solution (1.0 mol / L) was added to a 100 mL volumetric flask (made of polypropylene) 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 １９ F NMR measurements were performed. This measurement was performed twice for each concentration. １９ A calibration curve was created based on the integral ratio from the F NMR measurement results. NaF in each sample was quantified using this calibration curve.

[0199] <Carbon Content in Carbon-Based Substance> The crude material obtained in each example was analyzed by CHN.

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

[0201] <Amount of Organic Fluorine in Composition> The crude composition obtained in each example was analyzed by combustion ion chromatography.

[0202] <Presence or Absence of Fluorine Resin in Composition> The composition was subjected to NMR analysis to confirm whether or not a fluororesin was present.

[0203] In Examples 18 to 25, the following materials were used. Fluororesin C-1: PTFE (TFE homopolymer, manufactured by Kitamura Co., Ltd., KTL-2N) Fluororesin C-2: PVdF (VdF homopolymer, manufactured by BLD Pharmatech Ltd.), powder Reducing agent D-1: K (single element) (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 for 1 hour at room temperature (25°C) and 30 Hz. 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, followed by extraction three times with water. The aqueous layer was concentrated. The sample was diluted with water and CF ３A 100 mL sample was prepared using a 100 mL volumetric flask (made of polypropylene) containing 1.0 mL of COOK solution (1.0 mol / L). The yield of KF 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 measurement of the solid, organic layer, and aqueous layer obtained by filtration and extraction revealed that the composition contained 26 mass% fluoride ions, 53 mass% K as counter ions, and a carbon-based substance. The carbon-based substance was amorphous carbon with a carbon content of 67 mass%. The amount of organic fluorine in the carbon-based substance was 0.16 mass%. Fluororesin C-1 could not be confirmed by NMR.

[0205] Example 19 The same procedures as in Example 18 were repeated except that 8.8 equivalents of proton source E-1 were further added as a reactant and the reaction time was 10 minutes. The results are shown in Table 7.

[0206] Example 20 The same operations as in Example 18 were carried out except that fluororesin C-2 (256 mg, 4.0 mmol, calculated based on the molecular weight (64.03) of the constituent monomer VdF) 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 procedure of Example 18 was repeated except that 4.4 eq. (equivalent) 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 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)), 8.0 eq. of reducing agent D-2 (55 mg, 8 mmol), and 40 eq. of proton source E-1 (2.4 g, 40 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 for 1 hour at room temperature (25°C) and 30 Hz. 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 the mechanochemical treatment was in a slurry state at 25°C. NMR analysis of the solid, organic layer, and aqueous layer obtained by filtration and extraction revealed that it contained 3% by mass of fluoride ions, Li as counter ions, 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 procedures as in Example 22 were repeated except that the amount of proton source E-1 was changed to 16.0 eq. and 8.0 eq. of proton source E-3 was further added. The results are shown in Table 7.

[0210] Example 24 The procedure of Example 18 was repeated 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 procedure of Example 18 was repeated except that reducing agent D-5 was used instead of reducing agent D-1. The results are shown in Table 7.

[0212]

[0213] Example 26 The same procedures as in Example 18 were repeated, 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 resulting composition confirmed that KF was produced in a yield of 51%.

[0214] Example 27 Fluorine resin C-1 was mixed with C of 80% purity by mass. １２ F ２５ The procedure of Example 18 was repeated except that the amount of reducing agent D-1 was changed to I (149 mg) 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 96%.

[0215] Example 28 The same procedures as in Example 18 were carried out 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 for 60 minutes at room temperature (25°C) and 30 Hz. After completion, the jar was opened, and p-toluenesulfonyl chloride (R-SO ２ Cl, 2 mmol, 1.0 eq.) was added. The jar was closed, and mechanochemical treatment was carried out using a ball mill at room temperature (25°C) at 30 Hz for 5 minutes. After completion, the jar was opened, washed with ethyl acetate, and concentrated in vacuo. The resulting target sulfonyl fluoride (R-SO ２ The yield of F) was calculated using hexafluorobenzene as an internal standard. １９ The yield was 18% as determined by F NMR.

[0217] Example 30 The same procedures as in Example 29 were 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 To a glass reaction vessel were added 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). 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 procedure was the same as in Example 12, 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, after which its mass (X mg) was measured. The mass increase rate was calculated using the following formula, which was 20%: Increase rate (%) = (X - 298) / 298 × 100. The mass increase rate of the composition obtained in Example 1 was similarly calculated, which was 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 with the fluorine-containing compound, thereby obtaining a composition containing fluoride ions.

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. The production method according to any one of claims 1 to 4, 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. The method according to any one of claims 1 to 5, wherein the amount of the organic base used is 0.10 to 3 equivalents per equivalent of the fluorine-containing compound.

7. The method according to any one of claims 1 to 6, wherein the reducing agent has a standard electrode potential of -0.44 V or less.

8. The method according to any one of claims 1 to 7, wherein the reducing agent is at least one selected from the group consisting of Zn, Fe, Al, alkali metals and alkaline earth metals.

9. The method according to any one of claims 1 to 8, wherein the reducing agent is at least one selected from the group consisting of alkali metals and alkaline earth metals.

10. The method according to any one of claims 1 to 9, wherein the reducing agent is at least one selected from the group consisting of Li, Na, K, Mg and Ca.

11. The method according to any one of claims 1 to 10, wherein the reducing agent is at least one selected from the group consisting of K and Ca.

12. The method according to any one of claims 1 to 11, wherein the amount of the reducing agent used is 0.7 to 20 equivalents per equivalent of the fluorine-containing compound.

13. The method according to any one of claims 1 to 12, wherein the proton source is at least one selected from the group consisting of amines and alcohols.

14. The method according to any one of claims 1 to 13, wherein the proton source is at least one selected from the group consisting of ethylenediamine, methanol, ethanol, t-butyl alcohol, and 1-adamantanol.

15. The method of any one of claims 1 to 14, wherein the proton source is a primary amine.

16. The method of any one of claims 1 to 15, wherein the proton source is ethylenediamine.

17. The method according to any one of claims 1 to 16, wherein the amount of the proton source used is 8 to 50 equivalents per equivalent of the fluorine-containing compound.

18. The method according to any one of claims 1 to 17, wherein the fluorine-containing compound and the organic base are subjected to a mechanochemical treatment.

19. The method according to any one of claims 1 to 17, wherein the fluorine-containing compound and the reducing agent are subjected to a mechanochemical treatment.

20. The method according to any one of claims 1 to 17, wherein the fluorine-containing compound, the reducing agent, and the proton source are subjected to mechanochemical treatment.

21. The method according to any one of claims 1 to 20, wherein the fluorine-containing compound is solid at 25°C.

22. The method according to any one of claims 1 to 21, wherein the fluorine-containing compound is a fluorine-containing polymer.

23. The production method according to any one of claims 1 to 22, wherein the fluorine-containing compound is a fluorine-containing polymer containing polymerized 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. The method according to any one of claims 1 to 23, wherein the fluorine-containing compound is at least one selected from the group consisting of perfluororesins and polydifluoroethylenes.

25. The method according to any one of claims 1 to 24, wherein the fluorine-containing compound is at least one selected from the group consisting of polytetrafluoroethylene and polydifluoroethylene.

26. The method according to any one of claims 1 to 23, 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 production method according to any one of claims 1 to 26.

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

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

30. The fluorination method according to any one of claims 27 to 29, wherein the step of obtaining the composition and the step of fluorination are carried out continuously.

31. The fluorination method according to any one of claims 27 to 30, wherein 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 possessed by the object.

32. A fluorination method according to any one of claims 27 to 31, wherein the target substance is an organic compound having at least one atom selected from the group consisting of chlorine atoms and bromine atoms.

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

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

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

36. The composition according to any one of claims 33 to 35, wherein the fluoride ion content is 1 to 30 mass %.

37. The composition according to any one of claims 33 to 36, which is substantially free of fluororesin.

38. The composition of any one of claims 33 to 37, which is a fluorinating agent.

Images