Method for producing fluorine-containing compound, and fluorine-containing compound

Abstract

A method for producing a fluorine-containing compound, in which a fluorine-containing compound is obtained by fluorinating an organic compound in a liquid containing the organic compound having at least one fluorine-containing atom, said fluorine-containing compound being a fluoride having an average number of the fluorine-containing atoms per molecule of 0.01 or more.

Description

Technical Field

[0001] The present application relates to a method for producing a fluorine-containing compound and a fluorine-containing compound. Background Art

[0002] Various methods for fluorinating an organic compound having a fluorinable atom such as a hydrogen atom are known. For example, a method of using fluorine gas for fluorination is known.

[0003] Patent Document 1 discloses a method for fluorinating an organic compound by supplying fluorine gas to a liquid phase containing the organic compound having a fluorinable atom and an organic solvent.

[0004] Prior Art Documents

[0005] Patent Documents

[0006] Patent Document 1: WO 2000 / 056694 Summary of the Invention

[0007] Problems to be Solved by the Invention

[0008] Among fluorine-containing compounds, particularly, perfluorides in which all fluorinable atoms are substituted with fluorine atoms have high heat resistance and are useful as heat media, for example.

[0009] When producing a fluorine-containing compound belonging to a perfluoride as a target product by fluorination of a compound having a fluorinable atom, it is usually necessary to make the fluorination reaction conditions excessively severe. Specifically, examples include: extending the fluorination time; increasing the reaction temperature; increasing the reaction pressure; increasing the amount of fluorine gas when using fluorine gas for fluorination, etc.

[0010] However, as described above, if fluorination is carried out under excessively severe reaction conditions such as extending the fluorination time, side reactions such as decomposition reactions are likely to occur, and the yield of the fluorine-containing compound as the target product is likely to be low. In addition, the viscosity of a liquid containing a large amount of perfluoride tends to be high. Therefore, for example, when removing impurities by filtration after fluorination, the filtrate is likely to remain in the filtration device, etc., and the yield of the fluorine-containing compound as the target product is likely to be further reduced.

[0011] An object of one embodiment of the present invention is to provide a method for producing a fluorine-containing compound and a fluorine-containing compound, which can obtain the fluorine-containing compound as the target product in a high yield.

[0012] Solutions to the Problems

[0013] The present application includes the following aspects.

[0014] <1>A method for producing a fluorinated compound, wherein the fluorinated compound is obtained by fluorinating an organic compound containing at least one fluorinable atom in a liquid, and the fluorinated compound is a fluoride having an average number of the aforementioned fluorinable atoms per molecule of 0.01 or more.

[0015] <2>The method for producing a fluorinated compound according to <1>, wherein the average number of the aforementioned fluorinable atoms per molecule is 5 or less.

[0016] <3>The method for producing a fluorinated compound according to <1> or <2>, wherein the organic compound has a hydrogen atom as the aforementioned fluorinable atom.

[0017] <4>The method for producing a fluorinated compound according to any one of <1> to <3>, wherein the organic compound is fluorinated by introducing a gas containing fluorine gas into the aforementioned liquid.

[0018] <5>The method for producing a fluorinated compound according to any one of <1> to <4>, wherein the residence time of the aforementioned liquid in the reactor for the aforementioned fluorination is 200 hours or less.

[0019] <6>The method for producing a fluorinated compound according to any one of <1> to <5>, wherein the aforementioned liquid further contains a solvent.

[0020] <7>The method for producing a fluorinated compound according to <6>, wherein the mass of the aforementioned solvent is 10 times or less the mass of the organic compound.

[0021] <8>The method for producing a fluorinated compound according to any one of <1> to <7>, wherein the temperature of the aforementioned fluorination is 5 to 50 °C.

[0022] <9>The method for producing a fluorinated compound according to any one of <1> to <8>, wherein the number average molecular weight of the aforementioned organic compound is 800 to 28,000.

[0023] <10>A fluorinated compound having an average number of hydrogen atoms per molecule of 0.01 to 5 and a number average molecular weight of 1,000 to 30,000.

[0024] <11>The fluorinated compound according to <10>, which contains a fluoropolyether chain.

[0025] Advantages of the Invention

[0026] According to the present application, a method for producing a fluorinated compound and a fluorinated compound can be provided, and the production method can obtain the target fluorinated compound in a high yield. Detailed Embodiments

[0027] Hereinafter, the embodiments for implementing the embodiments of the present application will be described in detail. However, the embodiments of the present application are not limited to the following embodiments. In the following embodiments, the constituent elements (including element steps, etc.) are not essential unless otherwise explicitly stated. The same applies to numerical values and their ranges, which do not limit the embodiments of the present application.

[0028] In the present application, the numerical range represented by "~" means a range that respectively includes the numerical values described before and after "~" as the minimum value and the maximum value.

[0029] In the numerical ranges described step by step in the present application, the upper limit value or the lower limit value described by a certain numerical range can be replaced with the upper limit value or the lower limit value of other numerically described ranges. In addition, in the numerical ranges described in the present application, the upper limit value or the lower limit value described by a certain numerical range can be replaced with the value shown in the examples.

[0030] In the present application, the combination of two or more preferred modes is a more preferred mode.

[0031] In the present application, when there are multiple substances corresponding to each component, unless otherwise specified, it means the total amount of the multiple substances.

[0032] In the present application, when a compound is represented by a specific formula (X), the compound represented by the formula (X) is sometimes denoted as compound (X).

[0033] [Method for Producing Fluorine-Containing Compound]

[0034] In the method for producing a fluorine-containing compound according to an embodiment of the present application, a fluorine-containing compound is obtained by fluorinating an organic compound containing at least one fluorinable atom in a liquid, and the fluorine-containing compound is a fluoride having an average number of the above-mentioned fluorinable atoms per molecule of 0.01 or more.

[0035] Hereinafter, the organic compound containing at least one fluorinable atom is also referred to as "raw material compound", and the average number of the above-mentioned fluorinable atoms per molecule is also referred to as "atomic residue".

[0036] In the above method for producing a fluorine-containing compound, the target fluorine-containing compound can be obtained in a high yield.

[0037] Specifically, by setting the target substance as a fluoride having an atomic residue of 0.01 or more, even if the reaction conditions for fluorination are mild, it is easy to obtain the target substance. Therefore, by making the reaction conditions mild, side reactions are suppressed, and the yield of the fluorine-containing compound as the target substance becomes high. Also, by setting the target substance as a fluoride having an atomic residue of 0.01 or more, the viscosity of the liquid after fluorination is suppressed to be low. Therefore, when removing impurities by filtration, for example, the filtrate is not likely to remain in the filtration device, etc., and the yield of the fluorine-containing compound as the target substance becomes high.

[0038] <Atomic residue>

[0039] The above atomic residue is the average number of "fluorable atoms" in one molecule of the fluorine-containing compound as the target substance. For example, when the fluorine-containing compound obtained by fluorination of the raw material compound is a mixture of 3 molecules in which 1 fluorable atom remains in 10 molecules and 7 molecules in which all fluorable atoms are substituted by fluorine atoms, the atomic residue of the aforementioned fluorine-containing compound is 0.3. In this case, the 3 molecules in which 1 fluorable atom remains may be substances in which the fluorable atoms located at different positions among the fluorable atoms possessed by the raw material compound remain, or may be substances in which the fluorable atoms at the same position remain.

[0040] In addition, the fluorine-containing compound having an atomic residue of 0.3 is not limited to the above form. For example, it may be a mixture of 1 molecule in which 2 fluorable atoms remain in 10 molecules, 1 molecule in which 1 fluorable atom remains, and 7 molecules in which all fluorable atoms are substituted by fluorine atoms.

[0041] In other words, the fluorine-containing compound having an atomic residue of 0.01 or more may be a mixture of molecules having different numbers of remaining fluorable atoms. In particular, the fluorine-containing compound having an atomic residue of 0.01 or more and less than 1 is a mixture of molecules having 1 or more remaining fluorable atoms and molecules in which all fluorable atoms are substituted by fluorine atoms.

[0042] It should be noted that when the fluorine-containing compound has two or more types of fluorable atoms, the atomic residue is the average of the total of the aforementioned two or more types of fluorable atoms.

[0043] The above atomic residue is obtained by the following operation.

[0044] Specifically, for example, when the fluorable atom is a hydrogen atom, the atomic residue is obtained from the peak area of the hydrogen atom according to 1 H-NMR. In addition, according to 19 the peak area of the fluorine atom bonded to the carbon atom to which the fluorable atom is bonded obtained from F-NMR and 19The atomic residue number is determined by the ratio of the peak areas of fluorine atoms bonded to carbon atoms not bonded to fluorinable atoms obtained by F-NMR.

[0045] The atomic residue number is preferably 0.01 or more and 5 or less. If the fluorine-containing compound has an atomic residue number of 5 or less, even if it is not a perfluoride, that is, even if it is not a fluorine-containing compound with an atomic residue number of 0, it has high heat resistance and is useful as a heat medium, for example.

[0046] In other words, by fluorinating the starting compound in a liquid containing the starting compound, a fluorine-containing compound is obtained, and the fluorine-containing compound is a fluoride with an atomic residue number of 0.01 to 5, so that a fluorine-containing compound with high heat resistance can be obtained in high yield.

[0047] From the viewpoint of achieving both high yield and high heat resistance, the atomic residue number is more preferably 0.01 to 4, further preferably 0.01 to 1, and particularly preferably 0.01 to 0.5.

[0048] Examples of fluorinable atoms include a hydrogen atom, a bromine atom, an iodine atom, a chlorine atom, etc., and among them, a hydrogen atom is preferred.

[0049] The average number of "hydrogen atoms" in one molecule of the target fluorine-containing compound is preferably 0.01 or more, more preferably 0.01 to 5, further preferably 0.01 to 4, particularly preferably 0.01 to 1, and extremely preferably 0.01 to 0.5. Hereinafter, the average number of hydrogen atoms in one molecule of the target fluorine-containing compound is also referred to as "H residue number".

[0050] Examples of the method for controlling the atomic residue number and the H residue number include a method of adjusting the reaction conditions in the fluorination of the starting compound. Specific examples of the reaction conditions include the fluorination time, the reaction temperature, the reaction pressure, etc. In addition, when fluorinating the starting compound with fluorine gas, examples of the reaction conditions also include the amount and concentration of fluorine gas introduced into the liquid.

[0051] Furthermore, since the fluorinable atoms possessed by the starting compound are not fluorinated but remain, they become the fluorinable atoms possessed by the target product. Therefore, the atomic residue number and the H residue number can also be controlled by adjusting the number of fluorinable atoms and hydrogen atoms in each molecule of the starting compound.

[0052] <Fluorination reaction>

[0053] Examples of the method for fluorinating the starting compound in a liquid include, for example, the ECF method, the cobalt fluorination method, and a method of reacting it with fluorine. Among them, a method of reacting it with fluorine, which can advantageously fluorinate the starting compound, is preferred.

[0054] In a method of reacting a starting compound with fluorine in a liquid, for example, a gas containing fluorine gas is introduced into the liquid containing the starting compound.

[0055] Hereinafter, as an example of the fluorination reaction, a method of introducing a gas containing fluorine gas into a liquid containing a starting compound will be described, but it is not limited thereto.

[0056] The gas introduced into the liquid only needs to contain at least fluorine gas. The gas may consist of fluorine gas or may contain a gas other than fluorine gas.

[0057] Examples of the gas other than fluorine gas include inert gases. Examples of the inert gas include nitrogen, helium, neon, argon, etc., preferably nitrogen or helium, and preferably nitrogen from the viewpoint of suppressing the cost to a lower level.

[0058] From the viewpoint of easily controlling the atomic residue of the target substance, the content rate of fluorine gas in the whole gas is preferably 10% by volume or more, more preferably 15% by volume or more, further preferably 20% by volume or more, and particularly preferably 25% by volume or more. In addition, from the viewpoint of easily controlling the atomic residue of the target substance, the content rate of fluorine gas in the whole gas is preferably 60% by volume or less, more preferably 50% by volume or less, further preferably 40% by volume or less. From the above viewpoints, the content rate of fluorine gas in the whole gas is preferably 10 to 60% by volume, more preferably 15 to 50% by volume, further preferably 20 to 40% by volume, and particularly preferably 25 to 40% by volume.

[0059] Examples of the fluorination temperature of the starting compound include a range of -60°C or higher and lower than the boiling point of the starting compound, and may be in the range of -50 to 100°C, or may be in the range of -20 to 50°C. From the viewpoint of setting the atomic residue of the target substance in the above range, the fluorination temperature of the starting compound is preferably 5 to 50°C, more preferably 5 to 40°C, and further preferably 10 to 30°C.

[0060] Examples of the pressure in the fluorination of the starting compound include 0 to 2 MPa.

[0061] The fluorination of the starting compound may be in a batch mode or a continuous mode.

[0062] From the viewpoint of setting the atomic residue of the target substance in the above range, the residence time of the liquid containing the starting compound and into which fluorine gas has been introduced in the reactor for fluorinating the starting compound is preferably 200 hours or less, more preferably 190 hours or less, and further preferably 170 hours or less. Hereinafter, the residence time of the above liquid in the above reactor will also be referred to as the "residence time".

[0063] From the viewpoint of setting the atomic residue of the target substance within the aforementioned range, the residence time is preferably 0.3 hours or more, more preferably 0.6 hours or more, still more preferably 1.0 hours or more, particularly preferably 50 hours or more, extremely preferably 70 hours or more, and most preferably 100 hours or more. The residence time is preferably from 0.3 to 200 hours, more preferably from 0.6 to 200 hours, still more preferably from 1.0 to 200 hours, particularly preferably from 50 to 200 hours, extremely preferably from 70 to 200 hours, and most preferably from 100 to 200 hours.

[0064] When fluorinating the raw material compound in a continuous manner, the above residence time is calculated based on the flow rate of the above liquid and the volume of the reactor. Additionally, when fluorinating the raw material compound in a continuous manner, the residence time can be adjusted according to the flow rate of the above liquid and the length of the flow direction of the reactor, etc.

[0065] <Liquid>

[0066] The liquid contains at least the raw material compound and may further contain a solvent, other additives, etc. as needed. The raw material compound is an organic compound having at least one fluorinable atom.

[0067] (Raw material compound)

[0068] The raw material compound is not particularly limited as long as it is an organic compound having at least one fluorinable atom.

[0069] The raw material compound may have only one fluorinable atom or may have two or more. As the number of fluorinable atoms contained in one molecule of the raw material compound, for example, 1 to 200 can be cited, preferably 5 to 100, and more preferably 10 to 50. In other words, the average number of "fluorinable atoms" in one molecule of the raw material compound can be cited as 1 to 200, preferably 5 to 100, and more preferably 10 to 50.

[0070] Examples of the fluorinable atom include a hydrogen atom, a bromine atom, an iodine atom, chlorine, etc. Among them, a hydrogen atom is preferred. The raw material compound preferably has a hydrogen atom as the fluorinable atom.

[0071] As the number of hydrogen atoms contained in one molecule of the raw material compound, for example, 1 to 200 can be cited, preferably 5 to 100, and more preferably 10 to 50. In other words, the average number of hydrogen atoms in one molecule of the raw material compound can be cited as 1 to 200, preferably 5 to 100, and more preferably 10 to 50.

[0072] The number-average molecular weight of the starting compound may be, for example, from 800 to 100,000, preferably from 800 to 28,000, more preferably from 800 to 20,000, still more preferably from 800 to 10,000, particularly preferably from 1,000 to 10,000, very preferably from 1,000 to 8,000, and most preferably from 2,000 to 6,000, from the viewpoints of easy control of the number of atomic residues and obtaining a high yield by suppressing side reactions.

[0073] The number-average molecular weight of the above-mentioned starting compound is a value calculated from the molecular structure determined by 1 1H-NMR and 19 19F-NMR.

[0074] The starting compound is preferably a compound having a divalent or higher functional group containing at least one of an oxygen atom and a sulfur atom. Hereinafter, a divalent or higher functional group containing at least one of an oxygen atom and a sulfur atom is also referred to as a "specific functional group".

[0075] The specific functional group is a divalent or higher functional group containing at least one of an oxygen atom and a sulfur atom, preferably a divalent functional group containing at least one of an oxygen atom and a sulfur atom, and more preferably a divalent functional group containing an oxygen atom.

[0076] Examples of the specific functional group include an ester bond, an ether bond, an amide bond, a thioether bond, a thioester bond, a sulfonyl group, etc. In addition, examples of the specific functional group include a carbonyl group other than an ester bond and an amide bond.

[0077] The starting compound is preferably a compound having at least one selected from the group consisting of an ester bond, an ether bond, an amide bond, a thioether bond, a thioester bond, and a sulfonyl group as a specific functional group, more preferably a compound having at least one of an ester bond and an ether bond, still more preferably a compound having an ester bond, and particularly preferably a compound having both an ester bond and an ether bond.

[0078] The starting compound may be a compound having an ester bond as a specific functional group and having a fluorinable atom bonded to the carbon atom bonded to the carbonyl group of the ester bond. In addition, the starting compound may be a compound having an ester bond and an ether bond as specific functional groups and having a fluorinable atom bonded to the carbon atom bonded to the carbonyl group of the ester bond.

[0079] Examples of the starting compound include compounds represented by the following formula (1), compounds represented by the following formula (2), etc.

[0080] R A1 -O-(C=O)-R B1 …(1)

[0081] R B2 -(C=O)-O-R A2-O-(C=O)-R B3 …(2)

[0082] In formulas (1) and (2),

[0083] R A1 、R B1 、R B2 and R B3 are each independently a monovalent saturated hydrocarbon group, a halogenated monovalent saturated hydrocarbon group, a monovalent saturated hydrocarbon group containing a heteroatom, or a halogenated (monovalent saturated hydrocarbon group containing a heteroatom) group,

[0084] R A2 is a divalent saturated hydrocarbon group, a halogenated divalent saturated hydrocarbon group, a divalent saturated hydrocarbon group containing a heteroatom, or a halogenated (divalent saturated hydrocarbon group containing a heteroatom) group.

[0085] In the present application, the "monovalent saturated hydrocarbon group" can be any of a linear alkyl group, a branched alkyl group, and a cycloalkyl group. The "divalent saturated hydrocarbon group" can be any of a linear alkylene group, a branched alkylene group, and a cycloalkylene group. The linear alkyl group, the branched alkyl group, the linear alkylene group, and the branched alkylene group may contain an alicyclic structure.

[0086] In the present application, "halogenated" means that one or more hydrogen atoms present in the group are substituted by at least one halogen atom selected from fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. There may or may not be hydrogen atoms present in the group.

[0087] In the present application, the "halogenated monovalent saturated hydrocarbon group" means a group in which one or more hydrogen atoms present in the monovalent saturated hydrocarbon group are substituted by halogen atoms. The "halogenated divalent saturated hydrocarbon group" means a group in which one or more hydrogen atoms present in the divalent saturated hydrocarbon group are substituted by halogen atoms.

[0088] In the present application, the "heteroatom" means an atom other than a carbon atom and a hydrogen atom, and examples thereof include a nitrogen atom, an oxygen atom, and a sulfur atom.

[0089] In the present application, the "monovalent saturated hydrocarbon group containing a heteroatom" means a group containing a divalent heteroatom or a divalent group containing a heteroatom in the monovalent saturated hydrocarbon group. The "divalent saturated hydrocarbon group containing a heteroatom" means a group containing a divalent heteroatom or a divalent group containing a heteroatom in the divalent saturated hydrocarbon group. Examples of the divalent heteroatom include -O- and -S-. In addition, examples of the divalent group containing a heteroatom include -NH-, -C(=O)-, and -SO2-.

[0090] In the present application, the "halo (heteroatom-containing monovalent saturated hydrocarbon) group" means a group in which one or more hydrogen atoms in the above-mentioned heteroatom-containing monovalent saturated hydrocarbon group are substituted by halogen atoms. The "halo (heteroatom-containing divalent saturated hydrocarbon) group" means a group in which one or more hydrogen atoms in the above-mentioned heteroatom-containing divalent saturated hydrocarbon group are substituted by halogen atoms.

[0091] In formula (1), preferably, at least one of R A1 and R B1 contains a hydrogen atom. Further, in formula (2), preferably, at least one selected from the group consisting of R A2 、R B2 and R B3 contains a hydrogen atom.

[0092] 〔R A1 〕

[0093] In formula (1), R A1 is a monovalent saturated hydrocarbon group, a halo monovalent saturated hydrocarbon group, a heteroatom-containing monovalent saturated hydrocarbon group, or a halo (heteroatom-containing monovalent saturated hydrocarbon) group.

[0094] Examples of the monovalent saturated hydrocarbon group represented by R A1 include, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, pentyl, hexyl, octyl, 2-ethylhexyl, and cyclohexyl.

[0095] Examples of the halo monovalent saturated hydrocarbon group represented by R A1 are preferably haloalkyl groups. The halogen atoms contained in the halo monovalent saturated hydrocarbon group are preferably fluorine atoms, chlorine atoms, or bromine atoms, and more preferably fluorine atoms.

[0096] The heteroatom-containing monovalent saturated hydrocarbon group represented by R A1 is preferably a monovalent saturated hydrocarbon group containing an etheric oxygen atom (i.e., -O-), and more preferably an alkyl group containing an etheric oxygen atom.

[0097] Examples of the halo (heteroatom-containing monovalent saturated hydrocarbon) group represented by R A1 are preferably halo (heteroatom-containing alkyl) groups. The halogen atoms contained in the halo (heteroatom-containing monovalent saturated hydrocarbon) group are preferably fluorine atoms, chlorine atoms, or bromine atoms. The halo (heteroatom-containing monovalent saturated hydrocarbon) group is preferably a halo monovalent saturated hydrocarbon group containing an etheric oxygen atom, and more preferably a haloalkyl group containing an etheric oxygen atom.

[0098] From the viewpoint of excellent solubility in the solvents described later, the number of carbon atoms of R A1 is preferably 1 to 200, and more preferably 3 to 100.

[0099] Among them, from the viewpoint of excellent solubility in liquids, RA1 Preferably, it is represented by the following formula (A1). In other words, R A1 Preferably, it also has an ether bond, and more preferably contains at least one selected from the group consisting of a polyether chain and a fluoropolyether chain.

[0100] R 11 O-(R 12 O) m1 -R 13 -…(A1)

[0101] In formula (A1), R 11 is an alkyl group optionally having a fluorine atom, and R 12 are each independently an alkylene group optionally having a fluorine atom and having 1 to 6 carbon atoms, R 13 is an alkylene group optionally having a fluorine atom and having 1 to 6 carbon atoms, and m1 is an integer of 0 to 500.

[0102] In formula (A1), as R 11 , for example, an alkyl group and a fluoroalkyl group can be cited.

[0103] From the viewpoint of excellent solubility in the solvents described later, the number of carbon atoms of R 11 is preferably 1 to 100, more preferably 1 to 50, still more preferably 1 to 10, and particularly preferably 1 to 6.

[0104] R 11 The alkyl group represented can be a linear alkyl group, a branched alkyl group, or an alkyl group having a ring structure.

[0105] R 11 The fluoroalkyl group represented can be a linear fluoroalkyl group, a branched fluoroalkyl group, or a fluoroalkyl group having a ring structure.

[0106] Among them, R 11 is preferably an alkyl group, more preferably a linear alkyl group, and still more preferably a linear alkyl group having 1 to 6 carbon atoms.

[0107] In formula (A1), -(R 12 O) m1 - is preferably represented by the following formula (A2).

[0108] -[(R f1 O) k1 (R f2 O) k2 (R f3 O) k3 (R f4 O) k4 (R f5 O) k5 (R f6 O) k6-…(A2)

[0109] Among them,

[0110] R f1 is a fluoroalkylene group having 1 carbon atom,

[0111] R f2 is a fluoroalkylene group having 2 carbon atoms,

[0112] R f3 is a fluoroalkylene group having 3 carbon atoms,

[0113] R f4 is a fluoroalkylene group having 4 carbon atoms,

[0114] R f5 is a fluoroalkylene group having 5 carbon atoms,

[0115] R f6 is a fluoroalkylene group having 6 carbon atoms.

[0116] k1, k2, k3, k4, k5 and k6 each independently represent an integer of 0 or more, and k1 + k2 + k3 + k4 + k5 + k6 is an integer of 0 to 500.

[0117] From the viewpoint of excellent solubility in a liquid, k1 + k2 + k3 + k4 + k5 + k6 is preferably an integer of 1 to 500, more preferably an integer of 1 to 300, still more preferably an integer of 5 to 200, and particularly preferably an integer of 10 to 150.

[0118] It should be noted that the bonding order of (R f1 O) to (R f6 O) in formula (A2) is arbitrary. k1 to k6 in formula (A2) respectively represent the number of (R f1 O) to (R f6 O), and do not represent the configuration. For example, (R f5 O) k5 represents that the number of (R f5 O) is k5, and does not represent the block configuration structure of (R f5 O) k5 . Similarly, the recording order of (R f1 O) to (R f6 O) does not represent the bonding order of each unit.

[0119] R f3 ~R f6 Among them, the fluoroalkylene group can be a linear fluoroalkylene group, a branched fluoroalkylene group, or a fluoroalkylene group having a ring structure.

[0120] As R f1Specific examples of this include -CF2- and -CHF-.

[0121] As R f2 Specific examples of this include -CF2CF2-, -CF2CHF-, -CHFCF2-, -CHFCHF-, -CH2CF2- and -CH2CHF-.

[0122] As R f3 Specific examples of this include -CF2CF2CF2-, -CF2CHFCF2-, -CF2CH2CF2-, -CHFCF2CF2-, -CHFCHFCF2-, -CHFCHFCHF-, -CHFCH2CF2-, -CH2CF2CF2-, -CH2CHFCF2-, -CH2CH2CF2-, -CH2CF2CHF-, -CH2CHFCHF-, -CH2CH2CHF-, -CF(CF3)-CF2-, -CF(CHF2)-CF2-, -CF(CH2F)-CF2-, -CF(CH3)-CF2-, -CF(CF3)-CHF-, -CF(CHF2)-CHF-, -CF(CH2F)-CHF-, -CF(CH3)-CHF-, -CF(CF3)-CH2-, -CF(CHF2)-CH2-, -CF(CH2F)-CH2-, -CF(CH3)-CH2-, -CH(CF3)-CF2-, -CH(CHF2)-CF2-, -CH(CH2F)-CF2-, -CH(CH3)-CF2-, -CH(CF3)-CHF-, -CH(CHF2)-CHF-, -CH(CH2F)-CHF-, -CH(CH3)-CHF-, -CH(CF3)-CH2-, -CH(CHF2)-CH2- and -CH(CH2F)-CH2-.

[0123] As R f4Specific examples thereof include -CF2CF2CF2CF2-, -CF2CF2CF2CHF-, -CF2CF2CF2CH2-, -CF2CHFCF2CF2-, -CHFCHFCF2CF2-, -CH2CHFCF2CF2-, -CF2CH2CF2CF2-, -CHFCH2CF2CF2-, -CH2CH2CF2CF2-, -CHFCF2CHFCF2-, -CH2CF2CHFCF2-, -CF2CHFCHFCF2-, -CHFCHFCHFCF2-, -CH2CHFCHFCF2-, -CF2CH2CHFCF2-, -CHFCH2CHFCF2-, -CH2CH2CHFCF2-, -CF2CH2CH2CF2-, -CHFCH2CH2CF2-, -CH2CH2CH2CF2-, -CHFCH2CH2CHF-, -CH2CH2CH2CHF- and -cycloC4F6-.

[0124] As R f5 Specific examples thereof include -CF2CF2CF2CF2CF2-, -CHFCF2CF2CF2CF2-, -CH2CHFCF2CF2CF2-, -CF2CHFCF2CF2CF2-, -CHFCHFCF2CF2CF2-, -CF2CH2CF2CF2CF2-, -CHFCH2CF2CF2CF2-, -CH2CH2CF2CF2CF2-, -CF2CF2CHFCF2CF2-, -CHFCF2CHFCF2CF2-, -CH2CF2CHFCF2CF2-, -CH2CF2CF2CF2CH2- and -cycloC5F8-.

[0125] As R f6 Specific examples thereof include -CF2CF2CF2CF2CF2CF2-, -CF2CF2CHFCHF CF2CF2-, -CHFCF2CF2CF2CF2CF2-, -CHFCHFCHFCHFCHFCHF-, -CHFCF2CF2CF2CF2CH2-, -CH2CF2CF2CF2CF2CH2- and -cycloC6F 10 -.

[0126] Here, -cycloC4F6- refers to perfluorocyclobutane diyl, and specific examples thereof include perfluorocyclobutane-1,2-diyl. -cycloC5F8- refers to perfluorocyclopentane diyl, and specific examples thereof include perfluorocyclopentane-1,3-diyl. -cycloC6F 10- refers to perfluorocyclohexanediyl, and as a specific example thereof, perfluorocyclohexane-1,4-diyl can be cited.

[0127] Among them, -(R 12 O) m1 - preferably contains at least one selected from the group consisting of the structures represented by the following formulas (F1) to (F3), and more preferably contains the structure represented by formula (F2).

[0128] -(R f1 O) k1 -(R f2 O) k2 -…(F1)

[0129] -(R f2 O) k2 -(R f4 O) k4 -…(F2)

[0130] -(R f3 O) k3 -…(F3)

[0131] Among them, each symbol of formulas (F1) to (F3) is the same as that of the above formula (A2).

[0132] In formulas (F1) and (F2), the bonding order of (R f1 O) and (R f2 O), (R f2 O) and (R f4 O) is arbitrary respectively. For example, (R f1 O) and (R f2 O) can be alternately arranged, (R f1 O) and (R f2 O) can also be block arranged respectively, and in addition, it can be random. The same is true in formula (F2).

[0133] In formula (F1), k1 is preferably 1 to 30, more preferably 1 to 20. In addition, k2 is preferably 1 to 30, more preferably 1 to 20.

[0134] In formula (F2), k2 is preferably 1 to 30, more preferably 1 to 20. In addition, k4 is preferably 1 to 30, more preferably 1 to 20.

[0135] In formula (F3), k3 is preferably 1 to 30, more preferably 1 to 20.

[0136] In formula (A1), as R 13 , groups the same as the above R f1 to R f6 can be cited.

[0137] Among them, R 13 is preferably a fluoroalkylene group having 1 to 4 carbon atoms.

[0138] As specific examples of R A1 , the following structures can be cited, for example. * represents the site bonded to -O-, n1 represents an integer of 0 to 60, and n2 represents an integer of 0 to 500. As n1, 13 can be cited, for example, and as n2, 7 can be cited, for example.

[0139]

[0140] 〔R B1 〕

[0141] In formula (1), R B1 is a monovalent saturated hydrocarbon group, a halogenated monovalent saturated hydrocarbon group, a monovalent saturated hydrocarbon group containing a heteroatom, or a halogenated (monovalent saturated hydrocarbon containing a heteroatom) group.

[0142] As the monovalent saturated hydrocarbon group represented by R B1 , for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, pentyl, hexyl, octyl, 2-ethylhexyl, and cyclohexyl can be cited.

[0143] As the halogenated monovalent saturated hydrocarbon group represented by R B1 , a halogenated alkyl group is preferred. The halogen atom contained in the halogenated monovalent saturated hydrocarbon group is preferably a fluorine atom, a chlorine atom, or a bromine atom.

[0144] R B1 The monovalent saturated hydrocarbon group containing a heteroatom represented by is preferably a monovalent saturated hydrocarbon group containing an etheric oxygen atom (i.e., -O-), and more preferably an alkyl group containing an etheric oxygen atom. In other words, R B1 preferably further has an ether bond.

[0145] As the halogenated (monovalent saturated hydrocarbon containing a heteroatom) group represented by R B1 , a halogenated (alkyl group containing a heteroatom) is preferred. The halogen atom contained in the halogenated (monovalent saturated hydrocarbon containing a heteroatom) group is preferably a fluorine atom, a chlorine atom, or a bromine atom. The halogenated (monovalent saturated hydrocarbon containing a heteroatom) group is preferably a halogenated monovalent saturated hydrocarbon group containing an etheric oxygen atom, and more preferably a halogenated alkyl group containing an etheric oxygen atom.

[0146] From the viewpoint of excellent solubility in the solvents described later, the number of carbon atoms of R B1 is preferably 1 to 100, more preferably 2 to 50, and further preferably 3 to 20.

[0147] From the viewpoint of excellent solubility in the solvents described later, R B1 preferably contains at least one fluorine atom and preferably does not contain a hydrogen atom.

[0148] Among them, from the viewpoint of excellent solubility in the solvents described below, R B1 is preferably represented by the following formula (B1).

[0149] R 21 O-(R 22 O) m2 -R 23 -…(B1)

[0150] In formula (B1), R 21 is an alkyl group optionally having a fluorine atom, and each R 22 is independently an alkylene group optionally having a fluorine atom with 1 to 6 carbon atoms, R 23 is an alkylene group optionally having a fluorine atom with 1 to 6 carbon atoms, and m2 is an integer of 0 to 20.

[0151] In formula (B1), as R 21 , for example, an alkyl group and a fluoroalkyl group can be cited.

[0152] From the viewpoint of excellent solubility in the solvents described below, the number of carbon atoms of R 21 is preferably 1 to 50, more preferably 1 to 10, and further preferably 1 to 6.

[0153] R 21 The alkyl group represented can be a linear alkyl group, a branched alkyl group, or an alkyl group having a ring structure.

[0154] R 21 The fluoroalkyl group represented can be a linear fluoroalkyl group, a branched fluoroalkyl group, or a fluoroalkyl group having a ring structure.

[0155] Among them, R 21 is preferably a fluoroalkyl group, more preferably a linear fluoroalkyl group, further preferably a linear fluoroalkyl group with 1 to 6 carbon atoms, and particularly preferably a linear perfluoroalkyl group with 1 to 6 carbon atoms.

[0156] In formula (B1), -(R 22 O) m2 - is preferably represented by the above formula (A2).

[0157] In formula (B1), m2 is preferably 0 to 15, more preferably 0 to 10, further preferably 0 to 4, and particularly preferably 0 to 2.

[0158] In formula (B1), as R 23 , the same groups as those of the above R f1 to R f6 can be cited.

[0159] Among them, R23 Preferably a fluoroalkylene group having 1 to 3 carbon atoms, more preferably a perfluoroalkylene group having 1 to 3 carbon atoms.

[0160] As R B1 Specific examples include the following structures. * indicates the bonding site to -O-(C=O)-.

[0161]

[0162] 〔R A2 〕

[0163] In formula (2), R A2 is a divalent saturated hydrocarbon group, a halogenated divalent saturated hydrocarbon group, a divalent saturated hydrocarbon group containing a heteroatom, or a halogenated (divalent saturated hydrocarbon containing a heteroatom) group.

[0164] As the divalent saturated hydrocarbon group, halogenated divalent saturated hydrocarbon group, divalent saturated hydrocarbon group containing a heteroatom, or halogenated (divalent saturated hydrocarbon containing a heteroatom) group represented by R A2 can be exemplified by a group obtained by removing one hydrogen atom or halogen atom from the monovalent saturated hydrocarbon group, halogenated monovalent saturated hydrocarbon group, monovalent saturated hydrocarbon group containing a heteroatom, or halogenated (monovalent saturated hydrocarbon containing a heteroatom) group represented by R A1 in formula (1).

[0165] From the viewpoint of excellent solubility in the solvents described below, the number of carbon atoms of R A2 is preferably 1 to 200, more preferably 3 to 100.

[0166] Among them, from the viewpoint of excellent solubility in the solvents described below, R A2 is preferably represented by the following formula (A5). In other words, R A2 preferably further has an ether bond, and more preferably contains at least one selected from the group consisting of a polyether chain and a fluoropolyether chain.

[0167] -R 31 O-(R 32 O) m5 -R 33 -…(A5)

[0168] In formula (A5), R 31 and R 33 are each independently an alkylene group having 1 to 6 carbon atoms optionally having a fluorine atom, R 32 are each independently an alkylene group having 1 to 6 carbon atoms optionally having a fluorine atom, and m5 is an integer of 0 to 500.

[0169] In formula (A5), as R 31 and R 33, groups identical to R in formula (A1) can be listed independently of each other. 13 The same groups.

[0170] In formula (A5), as -(R 32 O) m5 -, groups identical to -(R 12 O) m1 - in formula (A1) can be listed.

[0171] As specific examples of R A2 , the following structures can be listed, for example. * indicates the bonding site to -O-, and n2 represents an integer of 0 to 500.

[0172]

[0173] 〔R B2 and R B3 〕

[0174] In formula (2), R B2 and R B3 are each independently a monovalent saturated hydrocarbon group, a halogenated monovalent saturated hydrocarbon group, a monovalent saturated hydrocarbon group containing a heteroatom, or a halogenated (monovalent saturated hydrocarbon containing a heteroatom) group.

[0175] As the monovalent saturated hydrocarbon group, halogenated monovalent saturated hydrocarbon group, monovalent saturated hydrocarbon group containing a heteroatom, or halogenated (monovalent saturated hydrocarbon containing a heteroatom) group represented by R B2 or R B3 , groups identical to the monovalent saturated hydrocarbon group, halogenated monovalent saturated hydrocarbon group, monovalent saturated hydrocarbon group containing a heteroatom, or halogenated (monovalent saturated hydrocarbon containing a heteroatom) group represented by R B1 in formula (1) can be listed.

[0176] As examples of the starting compound, the following compound (T1) etc. can also be listed.

[0177]

[0178] From the viewpoint of viscosity, the content rate of the starting compound contained in the liquid is preferably 10 to 100% by mass, more preferably 10 to 70% by mass, further preferably 15 to 70% by mass, and particularly preferably 20 to 50% by mass with respect to the whole liquid.

[0179] (Solvent)

[0180] The liquid may contain a solvent as needed. The solvent is not particularly limited as long as it can dissolve the starting compound.

[0181] From the viewpoint of excellent solubility of the starting compound and the fluorinated compound obtained by fluorinating the starting compound, the solvent preferably contains at least one selected from the group consisting of chlorinated solvents and fluorinated solvents other than chlorinated solvents, and more preferably contains chlorinated solvents. A chlorinated solvent is a solvent containing a chlorine atom. The chlorinated solvent preferably contains a fluorine atom in addition to the chlorine atom.

[0182] Examples of the chlorinated solvent include CClF2CClFCF2OCF2CClF2 (CFE-419), CH2ClCHClCH2OCF2CHFCl (HCFE-473), CF2ClCFClCHFOCF2CF2Cl (HCFE-428a,b), CFHClCFClCF2OCF2CF2Cl (HCFE-428c,d), CF2ClCHClCF2OCF2CF2Cl (HCFE-428e), 1,2,3,4-tetrachloroperfluorobutane (R-113), CF2Cl-CFCl-CFCl-O-CF2-CF2Cl (CFE-418), CClHFCClFCHFOCF2CClF2 (HCFE-437a,b), CClF2CClHCHFOCF2CClF2 (HCFE-437c), CClHFCClFCH2OCF2CClF2 (HCFE-446a), CF2ClCCl2CF2OCF2CFHCl (HCFE-427a,b), CF2HCClFCF2OCF2CF2Cl (HCFE-429), etc.

[0183] Examples of the fluorinated solvent other than chlorinated solvents include perfluoroalkanes (such as FC-72), perfluoroethers (such as FC-75, FC-77, etc.), perfluoropolyethers (trade names: Krytox, Fomblin, GALDEN, DEMNUM, etc.), inert fluids (trade name: Fluorinert), perfluorocarboxyl fluoride, etc.

[0184] From the viewpoint of increasing the yield of the fluorinated compound, the boiling point of the solvent is preferably 10 to 500 °C, more preferably 30 to 250 °C, and further preferably 50 to 150 °C.

[0185] From the viewpoint of increasing the yield of the fluorinated compound, the number of carbon atoms of the solvent is preferably 4 or more, more preferably 4 to 1,000, further preferably 4 to 500, particularly preferably 4 to 100, and most preferably 4 to 50.

[0186] From the viewpoint of improving the yield of the fluorinated compound, the molecular weight of the solvent is preferably 200 or more, more preferably 200 to 50,000, still more preferably 200 to 25,000, particularly preferably 200 to 10,000, and most preferably 200 to 1,000. In the case where there is a molecular weight distribution, the molecular weight represents the weight-average molecular weight (Mw). Mw is measured by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as an eluent and is measured in terms of polystyrene conversion.

[0187] The liquid contains a solvent, and the mass of the solvent is preferably 10 times or less, more preferably 5 times or less, still more preferably 3 times or less the mass of the starting compound. By making the mass of the solvent relative to the mass of the starting compound within the foregoing range, the amount of the solvent used is reduced, and the amount of the starting solution is reduced. Thus, there is an advantage that the reaction apparatus can be downsized. In addition, when the atomic residue of the fluorinated compound as the target is 0.01 or more, the viscosity of the fluorinated liquid can be suppressed to a low level. Therefore, the amount of the solvent can be reduced, and in the case of removing impurities by filtration, the filtrate is less likely to remain in the filtration device or the like, and the yield of the fluorinated compound as the target is increased.

[0188] (Other additives)

[0189] The liquid may contain other additives as needed. Examples of other additives include auxiliaries that promote the fluorination of the starting compound.

[0190] Examples of auxiliaries include compounds containing a C-H bond and compounds containing a carbon-carbon double bond other than the starting compound. Examples of compounds containing a C-H bond include benzene and toluene. Examples of compounds containing a carbon-carbon double bond include hexafluoropropene and hexafluorobutadiene. Among them, the auxiliary is preferably an aromatic hydrocarbon such as benzene or toluene.

[0191] It should be noted that in the present embodiment, since the atomic residue of the fluorinated compound as the target is 0.01 or more, even if the liquid does not contain an auxiliary, the fluorinated compound as the target can be obtained in a high yield in the direct fluorination with fluorine gas in the liquid. Therefore, the liquid may not contain the above-mentioned auxiliary.

[0192] <Fluorinated compound>

[0193] The fluorinated compound obtained by fluorination of the starting compound is a compound in which at least one fluorinable atom possessed by the starting compound is replaced by a fluorine atom and the atomic residue is 0.01 or more.

[0194] As described above, the fluorine-containing compound having 0.01 or more atomic residues may be a mixture of molecules having different numbers of fluorinable atoms. In particular, the fluorine-containing compound having 0.01 or more and less than 1 atomic residue is a mixture of a molecule having 1 or more fluorinable atoms and a molecule having no fluorinable atoms.

[0195] In addition, when there are a plurality of molecules having 1 or more fluorinable atoms, the plurality of molecules may have fluorinable atoms at different positions or at the same position with respect to each other.

[0196] For example, the fluorine-containing compound obtained by fluorinating the raw material compound represented by the following formula (1-1) may be a mixture of the molecules represented by the following formulas (2-1) to (2-4). It should be noted that in the following formulas (2-1) and (2-2), m5 and m6 represent integers from 0 to 13.

[0197]

[0198] The fluorine-containing compound is preferably a compound in which the average number of hydrogen atoms among the fluorinable atoms is 0.01 to 5 per molecule and the number average molecular weight is 1,000 to 30,000.

[0199] The average number of hydrogen atoms per molecule of the fluorine-containing compound is more preferably 0.01 to 4, further preferably 0.01 to 1, and particularly preferably 0.01 to 0.5.

[0200] Examples of the number average molecular weight of the fluorine-containing compound include 800 to 101,000. From the viewpoint of excellent solubility in a solvent, it is preferably 800 to 29,000, more preferably 800 to 21,000, further preferably 800 to 11,000, particularly preferably 1,000 to 11,000, extremely preferably 1,000 to 9,000, and most preferably 2,000 to 7,000. The number average molecular weight of the above-mentioned fluorine-containing compound is the number average value of the molecular weights of each molecule calculated from the molecular structure determined by 1 H-NMR and 19 F-NMR.

[0201] The fluorine-containing compound is preferably a compound having a specific functional group, and the specific functional group is a divalent or higher functional group containing at least one of an oxygen atom and a sulfur atom.

[0202] Details and preferred modes of the specific functional group are the same as those of the specific functional group in the aforementioned raw material compound.

[0203] When the starting compound is the compound represented by the aforementioned formula (1), the fluorine-containing compound is preferably a mixture of molecules with different numbers of hydrogen atoms among the compounds represented by the following formula (6). Additionally, when the starting compound is the compound represented by the aforementioned formula (2), the fluorine-containing compound is preferably a mixture of molecules with different numbers of hydrogen atoms among the compounds represented by the following formula (7).

[0204] R AF1 -O-(C=O)-R BF1 …(6)

[0205] R BF2 -(C=O)-O-R AF2 -O-(C=O)-R BF3 …(7)

[0206] In formulas (6) and (7),

[0207] R AF1 、R BF1 、R AF2 、R BF2 and R BF3 are respectively groups corresponding to R A1 、R B1 、R A2 、R B2 and R B3 ;

[0208] R A1 、R B1 、R A2 、R B2 and R B3 are each independently a group containing no hydrogen atom, R AF1 、R BF1 、R AF2 、R BF2 and R BF3 is the same group as R A1 、R B1 、R A2 、R B2 and R B3 ;

[0209] R A1 、R B1 、R A2 、R B2 and R B3 are each independently a group containing a hydrogen atom, R AF1 、R BF1 、R AF2 、R BF2 and R BF3 is R A1 、R B1 、R A2, R B2 and R B3 a group in which at least a part of the hydrogen atoms present in

[0210] The fluorine-containing compound may be a mixture of a molecule having no hydrogen atom and a molecule having one or more hydrogen atoms among the compounds represented by the aforementioned formula (6) or the compounds represented by the aforementioned formula (7).

[0211] In other words, for the compound represented by formula (6), it may be R A1 and R B1 a molecule in which all of the hydrogen atoms possessed by at least one of them are replaced by fluorine atoms and R A1 and R B1 a mixture of a molecule in which only a part of the hydrogen atoms possessed by at least one of them are replaced by fluorine atoms. Further, for the compound represented by formula (7), it may be R A2 , R B2 and R B3 a molecule in which all of the hydrogen atoms possessed by at least one of them are replaced by fluorine atoms and R A2 , R B2 and R B3 a mixture of a molecule in which only a part of the hydrogen atoms possessed by at least one of them are replaced by fluorine atoms.

[0212] 〔R AF1 〕

[0213] In formula (6), R AF1 is a group corresponding to R A1 .

[0214] When R A1 contains hydrogen atoms, R AF1 is the same group as R A1 or a group in which at least a part of the hydrogen atoms present in R A1 are replaced by fluorine atoms. When R A1 does not contain hydrogen atoms, R AF1 is the same group as R A1 .

[0215] From the viewpoint of excellent solubility in a solvent, R AF1 is preferably represented by the following formula (A3).

[0216] R 14 O-(R 15 O) m3 -R 16 -…(A3)

[0217] In formula (A3), R 14 is a fluoroalkyl group, R 15Each independently represents a fluoroalkylene group having 1 to 6 carbon atoms, R 16 is a fluoroalkylene group having 1 to 6 carbon atoms, and m3 is an integer from 0 to 500.

[0218] In formula (A3), R 14 corresponds to R in formula (A1). 11 . When R 11 contains a hydrogen atom, R 14 is the same group as R 11 or a group in which at least a part of the hydrogen atoms contained in R 11 are substituted with fluorine atoms. When R 11 does not contain a hydrogen atom, R 14 is the same as R 11 .

[0219] In formula (A3), -(R 15 O) m3 - corresponds to -(R 12 O) m1 - in formula (A1). When R 12 contains a hydrogen atom, R 15 is the same group as R 12 or a group in which at least a part of the hydrogen atoms contained in R 12 are substituted with fluorine atoms. When R 12 does not contain a hydrogen atom, R 15 is the same as R 12 .

[0220] In formula (A3), -(R 15 O) m3 - is preferably represented by the following formula (A4).

[0221] -[(R ff1 O) k7 (R ff2 O) k8 (R ff3 O) k9 (R ff4 O) k10 (R ff5 O) k11 (R ff6 O) k12 -…(A4)

[0222] Among them,

[0223] R ff1 is a fluoroalkylene group having 1 carbon atom,

[0224] R ff2 is a fluoroalkylene group having 2 carbon atoms,

[0225] R ff3 is a fluoroalkylene group having 3 carbon atoms,

[0226] R ff4 is a fluoroalkylene group having 4 carbon atoms,

[0227] R ff5 is a fluoroalkylene group having 5 carbon atoms,

[0228] R ff6 is a fluoroalkylene group having 6 carbon atoms.

[0229] k7, k8, k9, k10, k11 and k12 each independently represent an integer of 0 or more, and k7 + k8 + k9 + k10 + k11 + k12 is an integer of 0 to 500.

[0230] In formula (A4), R ff1 ~R ff6 corresponds to R f1 ~R f6 in formula (A2). For example, when R f1 contains a hydrogen atom, R ff1 is the same group as R f1 or a group in which at least a part of the hydrogen atoms contained in R f1 are substituted with fluorine atoms. When R f1 does not contain a hydrogen atom, R ff1 is the same as R f1 . The same applies to R ff2 ~R ff6 as R ff1 .

[0231] From the viewpoint of excellent solubility in a solvent, k7 + k8 + k9 + k10 + k11 + k12 is preferably an integer of 1 to 500, more preferably an integer of 1 to 300, still more preferably an integer of 5 to 200, and particularly preferably an integer of 10 to 150.

[0232] Among them, -(R 15 O) m3 - preferably contains at least one selected from the group consisting of the structures represented by the following formulas (G1) to (G3), and more preferably contains the structure represented by formula (G2).

[0233] -(R ff1 O) k7 -(R ff2 O) k8 -…(G1)

[0234] -(R ff2 O) k8 -(R ff4 O)k10 -…(G2)

[0235] -(R ff3 O) k9 -…(G3)

[0236] Among them, each symbol of formula (G1) to formula (G3) is the same as the above formula (A4).

[0237] In formula (G1) and formula (G2), (R ff1 O) and (R ff2 O), (R ff2 O) and (R ff4 O) can be bonded in any order. For example, (R ff1 O) and (R ff2 O) can be alternately arranged, (R ff1 O) and (R ff2 O) can also be block arranged respectively. In addition, it can be random. The same is true for formula (G2).

[0238] In formula (G1), k7 is preferably 1 to 30, more preferably 1 to 20. In addition, k8 is preferably 1 to 30, more preferably 1 to 20.

[0239] In formula (G2), k8 is preferably 1 to 30, more preferably 1 to 20. In addition, k10 is preferably 1 to 30, more preferably 1 to 20.

[0240] In formula (G3), k9 is preferably 1 to 30, more preferably 1 to 20.

[0241] In formula (A3), R 16 corresponds to R in formula (A1) 13 . When R 13 contains a hydrogen atom, R 16 is the same group as R 13 or a group in which at least a part of the hydrogen atoms contained in R 13 are replaced by fluorine atoms. When R 13 does not contain a hydrogen atom, R 16 is the same as R 13 .

[0242] As R 16 , groups similar to the above R ff1 ~R ff6 can be cited.

[0243] Among them, R 16 is preferably a fluoroalkylene group having 1 to 3 carbon atoms.

[0244] In formula (A3), m3 corresponds to m1 in formula (A1). m3 is the same as m1.

[0245] As R AF1 Specific examples of [R] include the following structures and structures in which a part of the fluorine atoms in the following structures are replaced by hydrogen atoms. * represents the site bonded to -O-, n1 represents an integer of 0 to 60, and n2 represents an integer of 0 to 500. As n1, for example, 13 can be cited, and as n2, for example, 7 can be cited.

[0246]

[0247] [R BF1

[0248] In formula (6), R BF1 is a group corresponding to R B1 .

[0249] When R B1 contains a hydrogen atom, R BF1 is the same group as R B1 or a group in which at least a part of the hydrogen atoms present in R B1 are replaced by fluorine atoms. When R B1 does not contain a hydrogen atom, R BF1 is the same group as R B1 .

[0250] From the viewpoint of excellent solubility in a solvent, R BF1 is preferably represented by the following formula (B2).

[0251] R 24 O-(R 25 O) m4 -R 26 -…(B2)

[0252] In formula (B2), R 24 is a fluoroalkyl group, R 25 are each independently a fluoroalkylene group having 1 to 6 carbon atoms, R 26 is a fluoroalkylene group having 1 to 6 carbon atoms, and m4 is an integer of 0 to 20.

[0253] In formula (B2), R 24 corresponds to R 21 in formula (B1). When R 21 contains a hydrogen atom, R 24 is the same group as R 21 or a group in which at least a part of the hydrogen atoms contained in R 21 are replaced by fluorine atoms. When R 21 does not contain a hydrogen atom, R 24 is the same as R 21 .​

[0254] In formula (B2), -(R 25 O) m4 - corresponds to -(R 22 O) m2 - in formula (B1). When R 22 contains a hydrogen atom, R 25 is the same group as R 22 or a group formed by substituting at least a part of the hydrogen atoms contained in R 22 with fluorine atoms. When R 22 does not contain a hydrogen atom, R 25 is the same as R 22 .

[0255] In formula (B2), -(R 25 O) m4 - is preferably represented by the above formula (A4).

[0256] In formula (B2), R 26 corresponds to R 23 in formula (B1). When R 23 contains a hydrogen atom, R 26 is the same group as R 23 or a group formed by substituting at least a part of the hydrogen atoms contained in R 23 with fluorine atoms. When R 23 does not contain a hydrogen atom, R 26 is the same as R 23 .

[0257] In formula (B2), m4 corresponds to m2 in formula (B1). m4 is the same as m2.

[0258] As a specific example of R BF1 , the following structures and the structures in which a part of the fluorine atoms in the following structures are replaced by hydrogen atoms can be cited. * indicates the bonding site with -O-(C=O)-.

[0259]

[0260] In formula (7), R AF2 is the group corresponding to R A2 .

[0261] When R A2 contains a hydrogen atom, R AF2 is the same group as R A2 or a group formed by substituting at least a part of the hydrogen atoms present in R A2 with fluorine atoms. When R A2 does not contain a hydrogen atom, R AF2To be the same group as R A2 Same group.

[0262] From the viewpoint of excellent solubility in a solvent, R AF2 Is preferably represented by the following formula (A6). In other words, R AF2 Preferably also has an ether bond.

[0263] -R 34 O-(R 35 O) m6 -R 36 -…(A6)

[0264] In formula (A6), R 34 And R 36 Are each independently a fluoroalkylene group having 1 to 6 carbon atoms, and R 35 Are each independently a fluoroalkylene group having 1 to 6 carbon atoms, and m6 is an integer of 0 to 500.

[0265] In formula (A6), R 34 And R 36 Correspond to R 31 And R 33 In formula (A5), respectively. When R 31 Contains a hydrogen atom, R 34 Is the same group as R 31 Or a group in which at least a part of the hydrogen atoms contained in R 31 Are replaced by fluorine atoms. When R 31 Does not contain a hydrogen atom, R 34 Is the same as R 31 When R 33 Contains a hydrogen atom, R 36 Is the same group as R 33 Or a group in which at least a part of the hydrogen atoms contained in R 33 Are replaced by fluorine atoms. When R 33 Does not contain a hydrogen atom, R 36 Is the same as R 34 Same.

[0266] In formula (A6), -(R 35 O) m6 - corresponds to -(R 32 O) m5 - in formula (A5). When R 32 Contains a hydrogen atom, R 35 Is the same group as R 32 Or a group in which at least a part of the hydrogen atoms contained in R 32 Are replaced by fluorine atoms. When R 32 Does not contain a hydrogen atom, R 35Same as R 32 Same.

[0267] In formula (A6), as R 34 and R 36 , groups the same as R in formula (A5) can be each independently listed. 31 and R 33 Same groups.

[0268] In formula (A6), as -(R 35 O) m6 -, groups the same as -(R 32 O) m5 - in formula (A5) can be listed.

[0269] As a specific example of R AF2 , structures such as the following structure and structures in which a part of the fluorine atoms in the following structure are replaced by hydrogen atoms can be listed. * indicates the bonding site to -O-, and n2 represents an integer from 0 to 500.

[0270]

[0271] 〔R BF2 and R BF3 〕

[0272] In formula (7), R BF2 and R BF3 are groups corresponding to R B2 and R B3 respectively.

[0273] When R B2 contains a hydrogen atom, R BF2 is the same group as R B2 or a group in which at least a part of the hydrogen atoms present in R B2 are replaced by fluorine atoms. When R B2 does not contain a hydrogen atom, R BF2 is the same group as R B2 .

[0274] When R B3 contains a hydrogen atom, R BF3 is the same group as R B3 or a group in which at least a part of the hydrogen atoms present in R B3 are replaced by fluorine atoms. When R B3 does not contain a hydrogen atom, R BF3 is the same group as R B3 .

[0275] R BF2 or R BF3The groups shown may include the same groups as R in formula (6). BF1 The same groups as those shown.

[0276] Examples

[0277] Hereinafter, the present application will be described more specifically by way of examples. However, the present application is not limited to the following examples as long as it does not depart from its gist. Examples 1-1 to 1-7, 2-1 to 2-4, and 3-1 to 3-3 are examples, and Examples 1-8 to 1-9 and 2-5 are comparative examples.

[0278] Hereinafter, CClF2CClFCF2OCF2CClF2 will be denoted as "CFE-419".

[0279] [Examples 1-1 to 1-9]

[0280] First, CFE-419 as the initial solvent was charged into a stainless steel reactor at the circulating liquid volume shown in the following table, and it was circulated in the circulation line at 300 L / hour.

[0281] Next, a raw material solution obtained by diluting the compound represented by the following formula (1-1) as the raw material compound with CFE-419 used as the solvent was fed into the circulation line at a flow rate such that the flow rate of the raw material compound was the raw material flow rate shown in the following table and the flow rate of the raw material solution was the raw material solution flow rate shown in the following table.

[0282] Next, fluorine gas diluted to 30% by volume with nitrogen was fed into the circulation line at the gas flow rate shown in the following table.

[0283] It should be noted that the temperature of the circulating liquid in the circulation line was adjusted to 20 °C using a condenser.

[0284] In addition, the circulating liquid was continuously withdrawn to keep the circulating liquid volume as shown in the following table.

[0285] The gas phase part of the reactor was cooled to -10 °C using a condenser, the condensate was returned to the reactor, and the gas was sent to the scrubbing tower.

[0286]

[0287] By the above operations, fluorination of the raw material compound was carried out to obtain a fluorinated compound, which was a fluoride of the raw material compound.

[0288] The residence time during fluorination is shown in Table 1. It should be noted that the mass of CFE-419 as the solvent was 2.33 times the mass of the raw material compound, and the pressure during fluorination was set at atmospheric pressure.

[0289] The number-average molecular weight of the starting compound was 4,236, and the number-average molecular weights of the fluorides obtained in Examples 1-1 to 1-9 were 4,956 to 5,046.

[0290] The H residue numbers and yields of the obtained fluorides are shown in Table 1.

[0291] The following operations were performed on the obtained fluoride for the heat resistance test.

[0292] As the heat resistance testing machine, a thermogravimetry-differential thermal analysis device (TG / DTA, manufactured by SHIMADZU Corporation, DTG-60) was used. The starting temperature was set at 25°C, and the temperature was raised to 500°C at a heating rate of 10°C / minute. The heat resistance was evaluated according to the following criteria. The results are shown in Table 1.

[0293] S: The temperature at which the weight loss is 50% is 230°C or higher

[0294] A: The temperature at which the weight loss is 50% is 220°C or higher and lower than 230°C

[0295] B: The temperature at which the weight loss is 50% is 215°C or higher and lower than 220°C

[0296] C: The temperature at which the weight loss is 50% is 210°C or higher and lower than 215°C

[0297] D: The temperature at which the weight loss is 50% is 200°C or higher and lower than 210°C

[0298] E: The temperature at which the weight loss is 50% is lower than 200°C

[0299] [Table 1]

[0300]

[0301] [Examples 2-1 to 2-5]

[0302] The flow rate of the starting solution was set at 0.100 kg / hour, the flow rate of the starting material was set at 0.030 kg / hour, the gas flow rate was set at 1200 NL / hour, the circulating liquid volume was set at 3.0 L, the residence time was set at 166 hours, and the temperature of the circulating liquid was adjusted to the temperature shown in the following table. Except for this, the same operations as in Examples 1-1 to 1-9 were performed to fluorinate the starting compound to obtain a fluorinated compound, which was a fluoride of the starting compound.

[0303] The mass of CFE-419 as the solvent was 2.33 times the mass of the starting compound, and the pressure during fluorination was set at atmospheric pressure.

[0304] The number-average molecular weight of the starting compound was 4,236, and the number-average molecular weights of the fluorides obtained in Examples 2-1 to 2-5 were 4,956 to 5,046.

[0305] The H residue number and the yield of the obtained fluoride are shown in Table 2.

[0306] In addition, for the obtained fluoride, a heat resistance test was carried out in the same manner as in Examples 1-1 to 1-9, and the heat resistance was evaluated. The results are also shown in Table 2.

[0307] [Table 2]

[0308]

[0309] [Examples 3-1 to 3-3]

[0310] The flow rate of the raw material solution was set to 0.100 kg / hour, the flow rate of the raw material was set to 0.030 kg / hour, the flow rate of the gas was set to 1200 NL / hour, the amount of the circulating liquid was set to 3.0 L, the residence time was set to 166 hours, the temperature of the circulating liquid was set to 20 °C, and the type of the raw material compound was changed to the types shown in the following table. Except for this, the same operations as in Examples 1-1 to 1-9 were carried out to fluorinate the raw material compound, and a fluorine-containing compound, which is a fluoride of the raw material compound, was obtained.

[0311] The mass of CFE-419 as the solvent was 2.33 times the mass of the raw material compound, and the pressure during fluorination was set to normal pressure.

[0312] It should be noted that in the following table, (1-2) refers to the compound represented by the following formula (1-2), (1-3) refers to the compound represented by the following formula (1-3), (1-4) refers to the compound represented by the following formula (1-4), and the number of units in the following formula is the average value.

[0313] The H residue number and the yield of the obtained fluoride are shown in Table 3. The number-average molecular weight of the raw material compound and the number-average molecular weight of the obtained fluoride are also shown in Table 3.

[0314] In addition, for the obtained fluoride, a heat resistance test was carried out in the same manner as in Examples 1-1 to 1-9, and the heat resistance was evaluated. The results are also shown in Table 3.

[0315]

[0316] [Table 3]

[0317]

[0318] As shown in Table 1, in Examples 1-1 to 1-7, 2-1 to 2-4, and 3-1 to 3-3, a fluorine-containing compound as the target product can be obtained in a high yield as compared with Examples 1-8 to 1-9 and 2-5.

[0319] Industrial applicability

[0320] The method for producing the fluorine-containing compound of the present application can produce the target fluorine-containing compound at a higher yield than before. The obtained fluorine-containing compound can be derivatized into fluorine-containing compounds having various functional groups (such as hydroxyl group, ethylenically unsaturated group, epoxy group, carboxyl group, etc.). In addition, the obtained fluorine-containing compound and the derivatized fluorine-containing compound can be used in surface treatment agents, emulsifiers, rubbers, surfactants, solvents, heat media, pharmaceuticals, pesticides, lubricating oils, their intermediates, and the like.

[0321] The disclosure of Japanese Patent Application No. 2022-185978 filed on November 21, 2022 is incorporated herein by reference in its entirety. All documents, patent applications, and technical standards described in this specification are incorporated herein by reference to the same extent as if each individual document, patent application, and technical standard were specifically and separately incorporated by reference.

Claims

1. A method for manufacturing a fluorine-containing compound, wherein, A fluorinated compound is obtained by fluorinating an organic compound containing an organo - compound having at least one fluorinable atom in a liquid, and the fluorinated compound is a fluoride in which the average number of the fluorinable atoms per molecule is 0.01 or more.

2. The method for producing a fluorine-containing compound according to claim 1, wherein, The average number of the fluorinable atoms per molecule is 5 or less.

3. The method for producing a fluorine-containing compound according to claim 1 or 2, wherein, The organic compound has a hydrogen atom as the fluorinable atom.

4. The method for producing a fluorine-containing compound according to claim 1 or 2, wherein, The organic compound is fluorinated by introducing a gas containing fluorine gas into the liquid.

5. The method for producing a fluorine-containing compound according to claim 1 or 2, wherein, The residence time of the liquid in the reactor for the fluorination is 200 hours or less.

6. The method for producing a fluorine-containing compound according to claim 1 or 2, wherein, The liquid further contains a solvent.

7. The method for producing a fluorine-containing compound according to claim 6, wherein, The mass of the solvent is 10 times or less the mass of the organic compound.

8. The method for producing a fluorine-containing compound according to claim 1 or 2, wherein, The temperature of the fluorination is 5 to 50 °C.

9. The method for producing a fluorine-containing compound according to claim 1 or 2, wherein, The number - average molecular weight of the organic compound is 800 to 28000.

10. A fluorinated compound in which the average number of hydrogen atoms per molecule is 0.01 to 5, and the number - average molecular weight is 1000 to 30000.

11. The fluorinated compound according to claim 10, which contains a fluoropolyether chain.

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