Method for producing fluorine-containing compound

Abstract

A method for producing a fluorine-containing compound, said method comprising introducing a fluorine-gas-containing gas into a composition containing an organic compound having at least one fluorinated atom inside a reactor having an inner surface that is inactive with respect to fluorine gas, thereby fluorinating the organic compound.

Description

Technical Field

[0001] This application relates to a method for manufacturing a fluorinated compound. Background Art

[0002] As a method for fluorinating an organic compound having at least one fluorinable atom, a method of direct fluorination using fluorine gas is known (for example, Patent Document 1). In the direct fluorination using fluorine gas, for example, a gas containing fluorine gas is introduced into a composition containing the organic compound inside a reactor. Thereby, the organic compound reacts with fluorine gas, and the fluorinable atoms possessed by the organic compound are replaced with fluorine atoms.

[0003] Prior Art Documents

[0004] Patent Documents

[0005] Patent Document 1: WO 2000 / 056694 Summary of the Invention

[0006] Problems to be Solved by the Invention

[0007] As a reactor used in the direct fluorination using fluorine gas, a container made of a metal such as nickel is usually used.

[0008] However, if direct fluorination is carried out using fluorine gas inside the above reactor, the fluorine gas introduced for fluorinating the organic compound sometimes reacts with the inner surface of the reactor. If the fluorine gas reacts with the inner surface of the reactor, the reactor may be corroded and at the same time, the fluorine gas is consumed, the amount of fluorine gas used for fluorinating the organic compound becomes less, and the fluorination rate becomes low.

[0009] An object of one embodiment of the present invention is to provide a method for manufacturing a fluorinated compound having a high fluorination rate when performing direct fluorination using fluorine gas inside a reactor.

[0010] Means for Solving the Problems

[0011] This application includes the following aspects.

[0012] <1> A method for manufacturing a fluorinated compound, comprising: inside a reactor having an inner surface that is inactive to fluorine gas, introducing a gas containing fluorine gas into a composition containing an organic compound having at least one fluorinable atom, thereby fluorinating the organic compound.

[0013] <2>The method for producing a fluorine-containing compound according to <1>, wherein when the reactor is filled with a mixed gas containing 20% by volume of fluorine gas and 80% by volume of nitrogen gas at a pressure of 0.100 MPa and maintained for 5 hours, the difference between the pressure at the time of filling and the pressure after the maintenance is 0.001 MPa or less.

[0014] <3>The method for producing a fluorine-containing compound according to <1> or <2>, wherein the inner surface that is inactive to fluorine gas contains a metal fluoride.

[0015] <4>The method for producing a fluorine-containing compound according to <3>, wherein the reactor is a container that is made inactive to fluorine gas by filling a gas containing fluorine gas inside a container having a metal element on its inner surface and maintaining it.

[0016] <5>The method for producing a fluorine-containing compound according to <1> or <2>, wherein the inner surface that is inactive to fluorine gas contains a fluororesin.

[0017] <6>The method for producing a fluorine-containing compound according to any one of <1> to <5>, wherein the reactor has a reactor main body and a surface layer, the reactor main body contains at least one element selected from the group consisting of nickel, copper, aluminum, chromium, iron, silver, titanium, and molybdenum, and the surface layer is located on the inner surface of the reactor main body and is inactive to fluorine gas.

[0018] <7>The method for producing a fluorine-containing compound according to any one of <1> to <6>, wherein the composition is a liquid at the temperature at which the fluorination is carried out.

[0019] <8>The method for producing a fluorine-containing compound according to any one of <1> to <7>, wherein the organic compound has a divalent or higher functional group containing at least one of an oxygen atom and a sulfur atom.

[0020] <9>The method for producing a fluorine-containing compound according to any one of <1> to <8>, wherein the organic compound has 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.

[0021] Effects of the Invention

[0022] According to the present application, a method for producing a fluorine-containing compound with a high fluorination rate during direct fluorination using fluorine gas inside a reactor can be provided. Detailed Description of the Invention

[0023] 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 expressly stated. The same applies to numerical values and their ranges, and the embodiments of the present application are not limited thereby.

[0024] In the present application, the numerical range represented by "~" means a range including the numerical values described before and after "~" as the minimum value and the maximum value, respectively.

[0025] In the numerical ranges described stepwise 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 another numerically described stepwise range. 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.

[0026] In the present application, the combination of two or more preferred modes is a more preferred mode.

[0027] 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.

[0028] 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).

[0029] [Method for producing a fluorine-containing compound]

[0030] The method for producing a fluorine-containing compound according to one embodiment of the present application includes: introducing a gas containing fluorine gas into a composition containing an organic compound having at least one fluorinable atom inside a reactor having an inner surface that is inactive to fluorine gas, thereby fluorinating the organic compound.

[0031] Hereinafter, the organic compound having at least one fluorinable atom is also referred to as "starting compound".

[0032] As described above, if direct fluorination is carried out using fluorine gas inside a metal reactor, the fluorine gas sometimes reacts with the inner surface of the reactor. And if the fluorine gas reacts with the inner surface of the reactor, the reactor is sometimes corroded, and at the same time, the fluorine gas is consumed by its reaction with the inner surface of the reactor, and the fluorination rate becomes low.

[0033] In contrast, in the above manufacturing method, direct fluorination is carried out using fluorine gas inside a reactor having an inner surface that is inactive to fluorine gas. Therefore, the corrosion of the reactor is suppressed, and the consumption of fluorine gas caused by the reaction with the inner surface of the reactor is also suppressed. As a result, the fluorination rate becomes high.

[0034] Here, to confirm whether the reactor for direct fluorination using fluorine gas is a "reactor having an inner surface that is inactive to fluorine gas", the following operation can be carried out.

[0035] Specifically, first, after blowing nitrogen gas into the interior of the reactor to be confirmed for 1 hour, a mixed gas containing 20% by volume of fluorine gas and 80% by volume of nitrogen gas is filled at a pressure of 0.100 MPa and maintained for 5 hours. And if the difference between the pressure at the time of filling the mixed gas, i.e., 0.100 MPa, and the pressure after maintaining for 5 hours is 0.001 MPa or less, the inner surface of the reactor is inactive to fluorine gas.

[0036] Hereinafter, the difference between the pressure at the time of filling the above-mentioned mixed gas and the pressure after maintaining for 5 hours is also referred to as the "pressure change amount".

[0037] The pressure change amount being 0.001 MPa or less means that fluorine gas is not consumed during the 5-hour maintenance. In other words, it means that the inner surface of the reactor is inactive to fluorine gas.

[0038] On the other hand, when the pressure after maintaining for 5 hours decreases compared to the pressure at the time of filling the mixed gas and the above-mentioned pressure change amount exceeds 0.001 MPa, it can be considered that during the 5-hour maintenance, fluorine gas reacts with the components of the inner surface of the reactor and fluorine gas is consumed. In other words, it can be considered that the inner surface of the reactor is not inactive to fluorine gas.

[0039] <Reactor>

[0040] The reactor having an inner surface that is inactive to fluorine gas is not particularly limited as long as the inner surface is inactive to fluorine gas, and examples thereof include a reactor having a metal fluoride on the inner surface and a reactor having a fluororesin on the inner surface.

[0041] The reactor may have a reactor body and a surface layer, and the surface layer is located on the inner surface of the reactor body and is inactive to fluorine gas. The reactor having an inner surface that is inactive to fluorine gas may have a surface layer containing a metal fluoride on the inner surface of the reactor body, or may have a surface layer containing a fluororesin on the inner surface of the reactor body.

[0042] The material of the reactor body is not particularly limited, and from the viewpoint of being able to be carried out under a wide range of temperature / pressure conditions, it is preferably a metal. The material of the reactor body may be a pure metal composed of a single metal element or an alloy containing two or more elements.

[0043] The reactor body may contain at least one element selected from the group consisting of nickel, copper, aluminum, chromium, iron, silver, titanium, and molybdenum. In particular, with respect to a reactor body containing at least one element selected from the group consisting of nickel, copper, aluminum, chromium, iron, silver, titanium, and molybdenum, if fluorine gas directly contacts the inner surface, the inner surface of the reactor body easily reacts with the fluorine gas. In contrast, by providing a surface layer that is inactive to fluorine gas on the inner surface of the reactor body, the reaction between the inner surface of the reactor body and the fluorine gas is suppressed.

[0044] From the viewpoints of availability and economy, the material of the reactor body is preferably nickel and stainless steel.

[0045] (Reactor with a metal fluoride-containing inner surface)

[0046] A reactor with a metal fluoride-containing inner surface is obtained, for example, by performing an operation of filling a container with a metal element on the inner surface with a gas containing fluorine gas and holding it. Hereinafter, the operation of filling the container with a gas containing fluorine gas and holding it will also be referred to as the "inner surface fluorination operation".

[0047] The container after the above inner surface fluorination operation becomes a container with an inner surface that is inactive to fluorine gas due to the inner surface being fluorinated. This container is used as a reactor.

[0048] Examples of the reactor belonging to the container after the above inner surface fluorination operation include a reactor having a reactor body and a surface layer, the surface layer being located on the inner surface of the reactor body and containing a metal fluoride and being inactive to fluorine gas.

[0049] The conditions of the inner surface fluorination operation are not particularly limited as long as the inner surface of the resulting reactor is inactive to fluorine gas.

[0050] The gas used in the inner surface fluorination operation only needs to contain at least fluorine gas. The gas may consist of fluorine gas or may contain gases other than fluorine gas.

[0051] Examples of the gas other than fluorine gas include, for example, an inert gas. Examples of the inert gas include nitrogen, helium, neon, argon, etc. Nitrogen or helium is preferred, and nitrogen is preferred from the viewpoint of suppressing the cost to a lower level.

[0052] From the viewpoint of obtaining a reactor having an inner surface that is inactive to fluorine gas, the fluorine gas concentration in the gas used for the inner surface fluorination operation is preferably 10% by volume or more, more preferably 15% by volume or more, and still more preferably 20% by volume or more. From the viewpoint of excellent safety, the fluorine gas concentration in the gas used for the inner surface fluorination operation is preferably 60% by volume or less, more preferably 50% by volume or less, and still more preferably 40% by volume or less. From the foregoing viewpoints, the fluorine gas concentration in the gas used for the inner surface fluorination operation is preferably 10 to 60% by volume, more preferably 15 to 50% by volume, and still more preferably 20 to 40% by volume.

[0053] From the viewpoint of obtaining a reactor having an inner surface that is inactive to fluorine gas, the pressure of the gas during filling in the inner surface fluorination operation is preferably 0.001 MPa or more, more preferably 0.010 MPa or more. From the viewpoint of excellent safety, the pressure of the gas during filling in the inner surface fluorination operation is preferably 1.000 MPa or less, more preferably 0.200 MPa or less. From the foregoing viewpoints, the pressure of the gas during filling in the inner surface fluorination operation is preferably 0.001 to 1.000 MPa, more preferably 0.010 to 0.200 MPa.

[0054] From the viewpoint of obtaining a reactor having an inner surface that is inactive to fluorine gas, the gas retention time in the inner surface fluorination operation is preferably 30 minutes or more, more preferably 1 hour or more. The upper limit of the gas retention time in the inner surface fluorination operation is not particularly limited. The gas retention time in the inner surface fluorination operation can be 72 hours or less, can be 50 hours or less, or can be 10 hours or less. The gas retention time in the inner surface fluorination operation is preferably 30 minutes to 72 hours, more preferably 1 hour to 50 hours or less, and still more preferably 1 hour to 10 hours.

[0055] The "container with a metal element in the inner surface" before the inner surface fluorination operation can be the container that is the reactor main body itself, or a container having a surface layer formed on the inner surface of the reactor main body.

[0056] The surface layer can be a layer made of the same material as the reactor main body, or a layer made of a material different from that of the reactor main body. As the surface layer, for example, a layer of a metal element not contained in the reactor main body alone, a layer of an alloy containing a metal element not contained in the reactor main body, etc. can be cited. Specifically, as the material of the surface layer, nickel, titanium, etc. can be cited.

[0057] When performing an inner surface fluorination operation on a container that is the reactor main body itself, a part of the inner surface of the reactor main body is fluorinated to form a surface layer that contains metal fluoride and is inactive to fluorine gas. Therefore, the surface layer that is inactive to fluorine gas contains metal fluoride obtained by fluorination of the metal elements contained in the reactor main body.

[0058] On the other hand, when performing an inner surface fluorination operation on a container having a surface layer formed on the inner surface of the reactor main body, at least a part of the aforementioned surface layer is fluorinated to form a surface layer that contains metal fluoride and is inactive to fluorine gas. Therefore, the surface layer that is inactive to fluorine gas contains metal fluoride obtained by fluorination of the metal elements contained in the surface layer before the inner surface fluorination operation. In other words, the metal fluoride contained in the surface layer that is inactive to fluorine gas can be a substance obtained by fluorination of the same metal element as the metal element contained in the reactor main body, or can be a substance obtained by fluorination of a different metal element.

[0059] Examples of the metal fluoride include fluorides of at least one element selected from the group consisting of nickel, copper, aluminum, chromium, iron, silver, titanium, and molybdenum.

[0060] It should be noted that the surface layer containing these metal element fluorides, i.e., the metal fluoride, may sometimes peel off due to, for example, contact with moisture in the air. Therefore, when using a reactor with a metal fluoride-containing inner surface to perform fluorination of a raw material compound, it is preferable that after the aforementioned inner surface fluorination operation, the raw material compound is fluorinated without allowing a gas containing moisture to contact the inner surface of the reactor. For example, it is preferable to perform the aforementioned inner surface fluorination operation and the fluorination of the raw material compound in the form of a series of operations.

[0061] (Reactor with a fluororesin-containing inner surface)

[0062] A reactor with a fluororesin-containing inner surface is obtained, for example, by forming a surface layer containing a fluororesin on the inner surface of the reactor main body. In other words, a reactor having a reactor main body and a surface layer can be obtained, the surface layer is located on the inner surface of the reactor main body and contains a fluororesin and is inactive to fluorine gas.

[0063] Examples of the reactor main body include the same main body as the reactor main body in the aforementioned reactor with a metal fluoride-containing inner surface.

[0064] Examples of the fluororesin include tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), polytetrafluoroethylene (PTFE), etc.

[0065] The method for forming a surface layer containing a fluororesin on the inner surface of the reactor main body is not particularly limited, and examples include heat molding of the fluororesin, etc.

[0066] <Composition>

[0067] The composition introduced into the interior of a reactor having an inner surface that is inert to fluorine gas is not particularly limited as long as it contains the starting compound, and can be any of a liquid, a gas, and a solid at the temperature at which the fluorination of the starting compound is carried out.

[0068] From the viewpoint of increasing the yield of the fluorinated compound, the composition is preferably a liquid at the temperature at which the fluorination of the starting compound is carried out.

[0069] The composition contains at least a starting compound, which is an organic compound having at least one fluorinable atom, and the composition may also contain a solvent, other additives, etc. as needed.

[0070] (Starting compound)

[0071] The starting compound is not particularly limited as long as it is an organic compound having at least one fluorinable atom.

[0072] Examples of the fluorinable atom include a hydrogen atom, a bromine atom, an iodine atom, etc.

[0073] The starting compound may have only one fluorinable atom or may have two or more. Examples of the number of fluorinable atoms contained in one molecule of the starting compound include, for example, 1 to 1,000, preferably 1 to 500, and more preferably 1 to 100.

[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 also include a carbonyl group, an imide bond, etc. 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 the specific functional group, more preferably a compound having at least one of an ester bond and an ether bond, further preferably a compound having an ester bond, and particularly preferably a compound having both an ester bond and an ether bond.

[0078] In particular, when the raw material compound has an ester bond and a fluorinable atom is bonded to the carbon atom bonded to the oxygen atom of the ester bond, the aforementioned fluorinable atom is less likely to be fluorinated.

[0079] On the other hand, in the present embodiment, the fluorination reaction is carried out inside a reactor having an inner surface that is inert to fluorine gas. Therefore, as the raw material compound, even if a compound having an ester bond and a fluorinable atom bonded to the carbon atom bonded to the oxygen atom of the ester bond is used, a high fluorination rate can be obtained in direct fluorination using fluorine gas.

[0080] In other words, the raw material compound may be a compound having an ester bond as a specific functional group and a fluorinable atom bonded to the carbon atom bonded to the oxygen atom of the ester bond. Additionally, the raw material compound may be a compound having an ester bond and an ether bond as specific functional groups and a fluorinable atom bonded to the carbon atom bonded to the oxygen atom of the ester bond.

[0081] The number average molecular weight of the raw material compound is not particularly limited, and examples thereof include 100 to 100,000. From the viewpoint of excellent solubility in the solvent described later, it is preferably 100 to 20,000, more preferably 300 to 10,000, and further preferably 400 to 6,000.

[0082] The number average molecular weight of the above-mentioned raw material compound is the number average value of the molecular weights of each molecule calculated from the molecular structure determined by 1 1H-NMR and 19 19F-NMR.

[0083] Examples of the raw material compound include compounds represented by the following formula (1), compounds represented by the following formula (2), and the like.

[0084] R A1 -O-(C=O)-R B1 …(1)

[0085] R B2 -(C=O)-O-R A2 -O-(C=O)-R B3 …(2)

[0086] In formulas (1) and (2),

[0087] 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 containing a heteroatom) group,

[0088] R A2is 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.

[0089] 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.

[0090] 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 a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. There may or may not be hydrogen atoms present in the group.

[0091] 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.

[0092] 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.

[0093] 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-.

[0094] In the present application, the "halogenated (monovalent saturated hydrocarbon containing a heteroatom) group" means a group in which one or more hydrogen atoms in the above-mentioned monovalent saturated hydrocarbon group containing a heteroatom are substituted by halogen atoms. The "halogenated (divalent saturated hydrocarbon containing a heteroatom) group" means a group in which one or more hydrogen atoms in the above-mentioned divalent saturated hydrocarbon group containing a heteroatom are substituted by halogen atoms.

[0095] In formula (1), preferably at least one of R A1 and R B1 contains a hydrogen atom. In addition, in formula (2), preferably at least one selected from the group consisting of R A2 , R B2 and R B3 contains a hydrogen atom.

[0096] 〔R A1 〕

[0097] In formula (1), R A1 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.

[0098] As the monovalent saturated hydrocarbon group represented by R A1 examples thereof include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group, a 2-ethylhexyl group, and a cyclohexyl group.

[0099] As the halogenated monovalent saturated hydrocarbon group represented by R A1 it is preferably a halogenated alkyl group. The halogen atom contained in the halogenated monovalent saturated hydrocarbon group is preferably a fluorine atom, a chlorine atom, or a bromine atom, and more preferably a fluorine atom.

[0100] R A1 The monovalent saturated hydrocarbon group containing a heteroatom represented 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.

[0101] As the halogenated (monovalent saturated hydrocarbon containing a heteroatom) group represented by R A1 it is preferably a halogenated (alkyl group containing a heteroatom). 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.

[0102] From the viewpoint of excellent solubility in the solvents described below, the number of carbon atoms of R A1 is preferably 1 to 200, and more preferably 3 to 100.

[0103] Among them, from the viewpoint of excellent solubility in the solvents described below, R A1 is preferably represented by the following formula (A1). In other words, R A1 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.

[0104] R 11 O-(R 12 O) m1 -R 13 -…(A1)

[0105] In formula (A1), R 11 is an alkyl group optionally having a fluorine atom, and R 12 are each independently an alkylene group having 1 to 6 carbon atoms optionally having a fluorine atom, and R 13is an alkylene group having 1 to 6 carbon atoms which may optionally have a fluorine atom, and m1 is an integer of 0 to 500.

[0106] In formula (A1), as R 11 , for example, an alkyl group and a fluoroalkyl group can be mentioned.

[0107] 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.

[0108] The alkyl group represented by R 11 can be a linear alkyl group, a branched alkyl group, or an alkyl group having a ring structure.

[0109] The fluoroalkyl group represented by R 11 can be a linear fluoroalkyl group, a branched fluoroalkyl group, or a fluoroalkyl group having a ring structure.

[0110] 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.

[0111] In formula (A1), -(R 12 O) m1 - is preferably represented by the following formula (A2).

[0112] -[(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)

[0113] Among them,

[0114] R f1 is an alkylene group having 1 carbon atom which may optionally have a fluorine atom,

[0115] R f2 is an alkylene group having 2 carbon atoms which may optionally have a fluorine atom,

[0116] R f3 is an alkylene group having 3 carbon atoms which may optionally have a fluorine atom,

[0117] R f4 is an alkylene group having 4 carbon atoms which may optionally have a fluorine atom,

[0118] R f5 is an optionally fluorine atom-containing alkylene group having 5 carbon atoms,

[0119] R f6 is an optionally fluorine atom-containing alkylene group having 6 carbon atoms.

[0120] 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.

[0121] From the viewpoint of excellent solubility in the solvents described later, 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.

[0122] 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 means that the number of (R f5 O) is k5, and does not represent the block configuration structure of (R f5 O) k5 . Similarly, the description order of (R f1 O) to (R f6 O) does not represent the bonding order of each unit.

[0123] R f3 to R f6 Among them, the optionally fluorine atom-containing alkylene group can be a linear alkylene group, a branched alkylene group, or a cyclic alkylene group having a ring structure.

[0124] As a specific example of R f1 , -CH2-, -CF2- and -CHF- can be cited.

[0125] As a specific example of R f2 , -CH2CH2-, -CF2CF2-, -CF2CHF-, -CHFCF2-, -CHFCHF-, -CH2CF2- and -CH2CHF- can be cited.

[0126] As a specific example of R f3Specific examples thereof include -CH2CH2CH2-, -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-.

[0127] As R f4 Specific examples thereof include -CH2CH2CH2CH2-, -CF2CF2CF2CF2-, -CF2CF2CF2CHF-, -CF2CF2CF2CH2-, -CF2CHFCF2CF2-, -CHFCHFCF2CF2-, -CH2CHFCF2CF2-, -CF2CH2CF2CF2-, -CHFCH2CF2CF2-, -CH2CH2CF2CF2-, -CHFCF2CHFCF2-, -CH2CF2CHFCF2-, -CF2CHFCHFCF2-, -CHFCHFCHFCF2-, -CH2CHFCHFCF2-, -CF2CH2CHFCF2-, -CHFCH2CHFCF2-, -CH2CH2CHFCF2-, -CF2CH2CH2CF2-, -CHFCH2CH2CF2-, -CH2CH2CH2CF2-, -CHFCH2CH2CHF-, -CH2CH2CH2CHF-, and -cycloC4F6-.

[0128] As R f5Specific examples thereof include -CH2CH2CH2CH2CH2-, -CF2CF2CF2CF2CF2-, -CHFCF2CF2CF2CF2-, -CH2CHFCF2CF2CF2-, -CF2CHFCF2CF2CF2-, -CHFCHFCF2CF2CF2-, -CF2CH2CF2CF2CF2-, -CHFCH2CF2CF2CF2-, -CH2CH2CF2CF2CF2-, -CF2CF2CHFCF2CF2-, -CHFCF2CHFCF2CF2-, -CH2CF2CHFCF2CF2-, -CH2CF2CF2CF2CH2-, and -cycloC5F8-.

[0129] As R f6 Specific examples thereof include -CH2CH2CH2CH2CH2CH2-, -CF2CF2CF2CF2CF2CF2-, -CF2CF2CHFCHFCF2CF2-, -CHFCF2CF2CF2CF2CF2-, -CHFCHFCHFCHFCHFCHF-, -CHFCF2CF2CF2CF2CH2-, -CH2CF2CF2CF2CF2CH2-, and -cycloC6F 10 -.

[0130] Here, -cycloC4F6- refers to a perfluorocyclobutane diyl, and specific examples thereof include perfluorocyclobutane-1,2-diyl. -cycloC5F8- refers to a perfluorocyclopentane diyl, and specific examples thereof include perfluorocyclopentane-1,3-diyl. -cycloC6F 10 - refers to a perfluorocyclohexane diyl, and specific examples thereof include perfluorocyclohexane-1,4-diyl.

[0131] 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).

[0132] -(R f1 O) k1 -(R f2 O) k2 -…(F1)

[0133] -(R f2 O) k2 -(R f4 O) k4 -…(F2)

[0134] -(R f3 O)k3 -…(F3)

[0135] Among them, each symbol in Formula (F1) to Formula (F3) is the same as that in the above Formula (A2).

[0136] In Formula (F1) and Formula (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. In addition, it can be random. The same applies to Formula (F2).

[0137] 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.

[0138] 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.

[0139] In Formula (F3), k3 is preferably 1 to 30, more preferably 1 to 20.

[0140] In Formula (A1), as R 13 , groups the same as the above R f1 to R f6 can be cited.

[0141] Among them, R 13 is preferably an alkylene group having 1 to 4 carbon atoms and optionally having a fluorine atom.

[0142] As a specific example of R A1 , for example, the following structures can be cited. * represents the bonding site with -O-, n1 is an integer from 0 to 60, and n2 represents an integer from 0 to 200.

[0143]

[0144] 〔R B1 〕

[0145] 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.

[0146] As R B1Examples of the monovalent saturated hydrocarbon group shown include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group, a 2-ethylhexyl group, and a cyclohexyl group.

[0147] As R B1 The halogenated monovalent saturated hydrocarbon group shown is preferably a halogenated alkyl group. The halogen atom contained in the halogenated monovalent saturated hydrocarbon group is preferably a fluorine atom, a chlorine atom, or a bromine atom.

[0148] R B1 The monovalent saturated hydrocarbon group containing a heteroatom shown is preferably a monovalent saturated hydrocarbon group containing an etheric oxygen atom (i.e., -O-), more preferably an alkyl group containing an etheric oxygen atom. In other words, R B1 Preferably further has an ether bond.

[0149] As R B1 The halogenated (monovalent saturated hydrocarbon containing a heteroatom) group shown is preferably a halogenated (alkyl group containing a heteroatom). 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, more preferably a halogenated alkyl group containing an etheric oxygen atom.

[0150] From the viewpoint of excellent solubility in the solvents described below, the number of carbon atoms of R B1 is preferably 1 to 100, more preferably 2 to 50, and further preferably 3 to 20.

[0151] From the viewpoint of excellent solubility in the solvents described below, R B1 preferably contains at least one fluorine atom and preferably does not contain a hydrogen atom.

[0152] Among them, from the viewpoint of excellent solubility in the solvents described below, R B1 is preferably represented by the following formula (B1).

[0153] R 21 O-(R 22 O) m2 -R 23 -…(B1)

[0154] In formula (B1), R 21 is an alkyl group optionally having a fluorine atom, R 22 are each independently an alkylene group having 1 to 6 carbon atoms optionally having a fluorine atom, R 23 is an alkylene group having 1 to 6 carbon atoms optionally having a fluorine atom, and m2 is an integer of 0 to 20.

[0155] In formula (B1), as R 21 , examples include an alkyl group and a fluoroalkyl group.

[0156] From the viewpoint of excellent solubility in the following solvents, R 21 preferably has 1 to 50 carbon atoms, more preferably 1 to 10 carbon atoms, and still more preferably 1 to 6 carbon atoms.

[0157] R 21 The alkyl group represented by R may be a linear alkyl group, a branched alkyl group, or an alkyl group having a ring structure.

[0158] R 21 The fluoroalkyl group represented by R may be a linear fluoroalkyl group, a branched fluoroalkyl group, or a fluoroalkyl group having a ring structure.

[0159] Among them, R 21 is preferably a fluoroalkyl group, more preferably a linear fluoroalkyl group, still more preferably a linear fluoroalkyl group having 1 to 6 carbon atoms, and particularly preferably a linear perfluoroalkyl group having 1 to 6 carbon atoms.

[0160] In formula (B1), -(R 22 O) m2 - is preferably represented by the above formula (A2).

[0161] In formula (B1), m2 is preferably 0 to 15, more preferably 0 to 10, still more preferably 0 to 4, and particularly preferably 0 to 2.

[0162] In formula (B1), as R 23 , the same groups as those of the above R f1 to R f6 can be mentioned.

[0163] Among them, R 23 is preferably a fluoroalkylene group having 1 to 3 carbon atoms, and more preferably a perfluoroalkylene group having 1 to 3 carbon atoms.

[0164] As specific examples of R B1 , the following structures can be mentioned, for example. * indicates the bonding site to the -O-(C=O)- bond.

[0165]

[0166] 〔R A2 〕

[0167] 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.

[0168] As R A2Examples of the divalent saturated hydrocarbon group, halogenated divalent saturated hydrocarbon group, heteroatom-containing divalent saturated hydrocarbon group, or halogenated (heteroatom-containing divalent saturated hydrocarbon) group include those obtained by removing one hydrogen atom or halogen atom from the monovalent saturated hydrocarbon group, halogenated monovalent saturated hydrocarbon group, heteroatom-containing monovalent saturated hydrocarbon group, or halogenated (heteroatom-containing monovalent saturated hydrocarbon) group represented by R in formula (1). A1 Examples of the divalent saturated hydrocarbon group, halogenated divalent saturated hydrocarbon group, heteroatom-containing divalent saturated hydrocarbon group, or halogenated (heteroatom-containing divalent saturated hydrocarbon) group include those obtained by removing one hydrogen atom or halogen atom from the monovalent saturated hydrocarbon group, halogenated monovalent saturated hydrocarbon group, heteroatom-containing monovalent saturated hydrocarbon group, or halogenated (heteroatom-containing monovalent saturated hydrocarbon) group represented by R in formula (1).

[0169] 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.

[0170] 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.

[0171] -R 31 O-(R 32 O) m5 -R 33 -…(A5)

[0172] In formula (A5), each of R 31 and R 33 is independently an alkylene group having 1 to 6 carbon atoms which may optionally have a fluorine atom, each of R 32 is independently an alkylene group having 1 to 6 carbon atoms which may optionally have a fluorine atom, and m5 is an integer of 0 to 500.

[0173] In formula (A5), examples of R 31 and R 33 include the same groups as R 13 in formula (A1).

[0174] In formula (A5), examples of -(R 32 O) m5 - include the same groups as -(R 12 O) m1 - in formula (A1).

[0175] Specific examples of R A2 include, for example, the following structures. * represents the bonding site to -O-, and n2 represents an integer of 0 to 200.

[0176]

[0177] 〔R B2 and R B3 〕

[0178] 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.

[0179] Examples of 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 include the same groups 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 B1 in formula (1).

[0180] Examples of the starting compound also include the following compound (T1) and the like.

[0181]

[0182] From the viewpoint of obtaining a high fluorination rate, the content of the starting compound contained in the composition is preferably 1 to 100% by mass, more preferably 3 to 100% by mass, particularly preferably 3 to 70% by mass, and extremely preferably 3 to 50% by mass, relative to the whole composition.

[0183] (Solvent)

[0184] The composition may contain a solvent as needed. The solvent is not particularly limited as long as it can dissolve the starting compound.

[0185] From the viewpoint of excellent solubility of the starting compound and the fluorinated compound formed from the starting compound, the solvent preferably contains at least one selected from the group consisting of a chlorine-containing solvent and a fluorine-containing solvent other than the chlorine-containing solvent, and more preferably contains a chlorine-containing solvent. The chlorine-containing solvent is a solvent containing a chlorine atom. The chlorine-containing solvent preferably contains a fluorine atom in addition to the chlorine atom.

[0186] Examples of the chlorine-containing solvents 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.

[0187] Examples of the fluorine-containing solvents other than the chlorine-containing solvents include perfluoroalkanes (such as FC-72), perfluoroethers (such as FC-75, FC-77), perfluoropolyethers (trade names: Krytox, Fomblin, GALDEN, DEMNUM, etc.), inert fluids (trade name: Fluorinert), perfluorocarboxylic acid fluorides, etc.

[0188] From the viewpoint of improving the yield of the fluorine-containing 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.

[0189] From the viewpoint of improving the yield of the fluorine-containing 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.

[0190] From the viewpoint of improving the yield of the fluorine-containing compound, the molecular weight of the solvent is preferably 200 or more, more preferably 200 to 50,000, further 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.

[0191] (Other additives)

[0192] The composition may contain other additives as needed. As other additives, for example, an auxiliary agent that promotes the fluorination of the raw material compound can be cited.

[0193] As the auxiliary agent, for example, a compound containing a C-H bond and a compound containing a carbon-carbon double bond other than the raw material compound can be cited. As the compound containing a C-H bond, benzene, toluene, etc. can be cited. As the compound containing a carbon-carbon double bond, hexafluoropropene, hexafluorobutadiene, etc. can be cited. Among them, the auxiliary agent is preferably an aromatic hydrocarbon such as benzene or toluene.

[0194] <Fluorination reaction>

[0195] The gas introduced into the composition only needs to contain at least fluorine gas. The gas may consist of fluorine gas or may contain a gas other than fluorine gas.

[0196] As the gas other than fluorine gas, for example, an inert gas can be cited. As the inert gas, nitrogen, helium, neon, argon, etc. can be cited. Nitrogen or helium is preferred, and nitrogen is preferred from the viewpoint of suppressing the cost to a lower level.

[0197] From the viewpoint of obtaining a high fluorination rate, the content rate of fluorine gas in the whole gas is preferably 10% by volume or more, more preferably 15% by volume or more, and further preferably 20% by volume or more. In addition, from the viewpoint of excellent safety, the content rate of fluorine gas in the whole gas is preferably 60% by volume or less, more preferably 50% by volume or less, and 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, and further preferably 20 to 40% by volume.

[0198] As the reaction temperature in the fluorination of the raw material compound, for example, a range of -60°C or higher and lower than the boiling point of the raw material compound can be cited. It can be in the range of -50 to 100°C, or can also be in the range of -20 to 50°C.

[0199] As the pressure in the fluorination of the raw material compound, for example, 0 to 2 MPa can be cited.

[0200] The fluorination of the raw material compound can be in a batch mode or a continuous mode.

[0201] From the viewpoint of improving the fluorination rate, the residence time of the composition containing the raw material compound and into which fluorine gas is introduced in the reactor for fluorinating the raw material compound is preferably 200 hours or less, more preferably 190 hours or less, further preferably 170 hours or less, particularly preferably 150 hours or less, and extremely preferably 100 hours or less. Hereinafter, the residence time of the above composition in the above reactor is also referred to as the "residence time".

[0202] From the viewpoint of improving the fluorination rate, the residence time is preferably 0.3 hours or more, more preferably 0.6 hours or more, further preferably 1 hour or more, particularly preferably 2 hours or more, and most preferably 3 hours or more. The residence time is preferably from 0.3 to 200 hours, more preferably from 0.6 to 200 hours, further preferably from 1 to 200 hours, particularly preferably from 1 to 190 hours, further preferably from 1 to 170 hours, most preferably from 2 to 150 hours, and most preferably from 3 to 100 hours.

[0203] When the fluorination of the starting compound is carried out in a continuous manner, the residence time is calculated based on the flow rate of the composition and the volume of the reactor. In addition, when the fluorination of the starting compound is carried out in a continuous manner, the residence time can be adjusted based on the flow rate of the composition and the length of the flow path in the reactor, etc.

[0204] The fluorination rate in the fluorination of the starting compound is preferably 80% or more, more preferably 85% or more, further preferably 87% or more, and particularly preferably 100%.

[0205] The above-mentioned fluorination rate is determined by the following operation.

[0206] Specifically, by NMR measurement using an internal standard substance of the reaction product, assuming that the reaction product is a compound in which all the fluorinable atoms are completely fluorinated, the fluorination rate is calculated using the following formula.

[0207] Formula: Fluorination rate (%) = {1 - (number of fluorinable atoms per molecule of reaction product) / (number of fluorinable atoms per molecule of starting compound)} × 100

[0208] <Fluorine-containing compound>

[0209] The fluorine-containing 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.

[0210] The fluorine-containing compound is preferably a compound in which all the fluorinable atoms possessed by the starting compound are replaced by fluorine atoms.

[0211] When the starting compound is the compound represented by the foregoing formula (1), the fluorine-containing compound is preferably the compound represented by the following formula (3). In addition, when the starting compound is the compound represented by the foregoing formula (2), the fluorine-containing compound is preferably the compound represented by the following formula (4).

[0212] R AF1 -O-(C=O)-R BF1 …(3)

[0213] R BF2 -(C=O)-O-RAF2 -O-(C=O)-R BF3 …(4)

[0214] In Formulas (6) and (7),

[0215] 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 ;

[0216] When 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 are the same groups as R A1 、R B1 、R A2 、R B2 and R B3 ;

[0217] When 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 the group formed by replacing all hydrogen atoms present in R A1 、R B1 、R A2 、R B2 and R B3 with fluorine atoms.

[0218] 〔R AF1 〕

[0219] In Formula (3), R AF1 is the group corresponding to R A1 ;

[0220] When R A1 contains a hydrogen atom, R AF1 is R A1A group in which all hydrogen atoms present in R are replaced by fluorine atoms. A1 When R does not contain hydrogen atoms, AF1 R is the same group as A1 R.

[0221] From the viewpoint of excellent solubility in a solvent, R AF1 is preferably represented by the following formula (A3).

[0222] R 14 O-(R 15 O) m3 -R 16 -…(A3)

[0223] In formula (A3), R 14 is a perfluoroalkyl group, each R 15 is independently a perfluoroalkylene group having 1 to 6 carbon atoms, R 16 is a perfluoroalkylene group having 1 to 6 carbon atoms, and m3 is an integer of 0 to 500.

[0224] In formula (A3), R 14 corresponds to R in formula (A1) 11 . When R 11 contains hydrogen atoms, R 14 is a group in which all hydrogen atoms contained in R 11 are replaced by fluorine atoms. When R 11 does not contain hydrogen atoms, R 14 is the same as R 11 .

[0225] In formula (A3), -(R 15 O) m3 - corresponds to -(R 12 O) m1 - in formula (A1). When R 12 contains hydrogen atoms, R 15 is a group in which all hydrogen atoms contained in R 12 are replaced by fluorine atoms. When R 12 does not contain hydrogen atoms, R 15 is the same as R 12 .

[0226] In formula (A3), -(R 15 O) m3 - is preferably represented by the following formula (A4).

[0227] -[(R ff1 O) k7 (R ff2 O) k8 (R ff3 O) k9 (Rff4 O) k10 (R ff5 O) k11 (R ff6 O) k12 -…(A4)

[0228] Among them,

[0229] R ff1 is a perfluoroalkylene group having 1 carbon atom,

[0230] R ff2 is a perfluoroalkylene group having 2 carbon atoms,

[0231] R ff3 is a perfluoroalkylene group having 3 carbon atoms,

[0232] R ff4 is a perfluoroalkylene group having 4 carbon atoms,

[0233] R ff5 is a perfluoroalkylene group having 5 carbon atoms,

[0234] R ff6 is a perfluoroalkylene group having 6 carbon atoms.

[0235] 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.

[0236] 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 a group formed by substituting all hydrogen atoms contained in R f1 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 well as R ff1 .

[0237] 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.

[0238] 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).

[0239] -(R ff1 O) k7 -(R ff2 O) k8 -…(G1)

[0240] -(R ff2 O) k8 -(R ff4 O) k10 -…(G2)

[0241] -(R ff3 O) k9 -…(G3)

[0242] Among them, each symbol in formulas (G1) to (G3) is the same as that in the above formula (A4).

[0243] In formulas (G1) and (G2), the bonding order of (R ff1 O) and (R ff2 O), (R ff2 O) and (R ff4 O) is arbitrary respectively. 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, and in addition, it can be random. The same is true for formula (G2).

[0244] 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.

[0245] 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.

[0246] In formula (G3), k9 is preferably 1 to 30, more preferably 1 to 20.

[0247] In formula (A3), R 16 corresponds to R 13 in formula (A1). When R 13 contains a hydrogen atom, R 16 is a group in which all 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 .

[0248] As R 16 , groups similar to the above R ff1 ~R ff6 can be enumerated.

[0249] Among them, R 16 is preferably a perfluoroalkylene group having 1 to 3 carbon atoms.

[0250] In formula (A3), m3 corresponds to m1 in formula (A1). m3 is the same as m1.

[0251] As specific examples of R AF1 , for example, the following structures can be enumerated. * represents the bonding site to -O-, n1 represents an integer from 0 to 60, and n2 represents an integer from 0 to 200.

[0252]

[0253] [R BF1

[0254] In formula (3), R BF1 is a group corresponding to R B1 .

[0255] When R B1 contains a hydrogen atom, R BF1 is a group in which all 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 .

[0256] From the viewpoint of excellent solubility in a solvent, R BF1 is preferably represented by the following formula (B2).

[0257] R 24 O-(R 25 O) m4 -R 26 -…(B2)

[0258] In formula (B2), R 24 is a perfluoroalkyl group, R 25 are each independently a perfluoroalkylene group having 1 to 6 carbon atoms, R 26 is a perfluoroalkylene group having 1 to 6 carbon atoms, and m4 is an integer from 0 to 20.

[0259] In formula (B2), R 24 corresponds to R 21 in formula (B1). When R 21 contains a hydrogen atom, R 24 is R 21 ​A group in which all hydrogen atoms contained in R are replaced by fluorine atoms. R 21 When R contains no hydrogen atoms, R 24 is the same as R 21 .

[0260] In formula (B2), -(R 25 O) m4 - corresponds to -(R 22 O) m2 - in formula (B1). R 22 When R contains hydrogen atoms, R 25 is a group in which all hydrogen atoms contained in R 22 are replaced by fluorine atoms. R 22 When R contains no hydrogen atoms, R 25 is the same as R 22 .

[0261] In formula (B2), -(R 25 O) m4 - is preferably represented by the above formula (A4).

[0262] In formula (B2), R 26 corresponds to R 23 in formula (B1). R 23 When R contains hydrogen atoms, R 26 is a group in which all hydrogen atoms contained in R 23 are replaced by fluorine atoms. R 23 When R contains no hydrogen atoms, R 26 is the same as R 23 .

[0263] In formula (B2), m4 corresponds to m2 in formula (B1). m4 is the same as m2.

[0264] As a specific example of R BF1 , the following structures can be listed, for example. * indicates the bonding site with -O-(C=O)-.

[0265]

[0266] [R AF2

[0267] In formula (4), R AF2 is a group corresponding to R A2 .

[0268] R A2 When R contains hydrogen atoms, R AF2 is a group in which all hydrogen atoms present in R A2 are replaced by fluorine atoms. R A2 When R contains no hydrogen atoms, R AF2 is the same as R​A2 Same group.

[0269] 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 further has an ether bond.

[0270] -R 34 O-(R 35 O) m6 -R 36 -…(A6)

[0271] In formula (A6), R 34 And R 36 Are each independently a perfluoroalkylene group having 1 to 6 carbon atoms, and R 35 Are each independently a perfluoroalkylene group having 1 to 6 carbon atoms, and m6 is an integer of 0 to 500.

[0272] 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 a group in which all 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 a group in which all 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 .

[0273] 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 a group in which all hydrogen atoms contained in R 32 Are replaced by fluorine atoms. When R 32 Does not contain a hydrogen atom, R 35 Is the same as R 32 .

[0274] In formula (A6), as R 34 And R 36, the same groups as R in formula (A5) can be listed independently of each other. 31 and R 33 can be the same groups.

[0275] In formula (A6), as -(R 35 O) m6 -, the same groups as -(R 32 O) m5 - in formula (A5) can be listed.

[0276] As specific examples of R AF2 , for example, the following structures can be listed. * represents the bonding site with -O-, and n2 represents an integer from 0 to 200.

[0277]

[0278] 〔R BF2 and R BF3 〕

[0279] In formula (4), R BF2 and R BF3 are groups corresponding to R B2 and R B3 respectively.

[0280] When R B2 contains a hydrogen atom, R BF2 is a group in which all 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 .

[0281] When R B3 contains a hydrogen atom, R BF3 is a group in which all 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 .

[0282] The groups represented by R BF2 or R BF3 can be the same groups as the group represented by R BF1 in formula (3).

[0283] The number average molecular weight of the fluorine-containing compound is not particularly limited, and for example, it can be 100 to 101,000. From the viewpoint of excellent solubility in a solvent, it is preferably 100 to 21,000, more preferably 300 to 11,000, and further preferably 400 to 7,000.

[0284] The number-average molecular weight of the fluorine-containing compound described above is the number-average value of the molecular weights of each molecule calculated from the molecular structure determined by 1 1H-NMR and 19 19F-NMR.

[0285] Examples

[0286] 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 exceed the gist thereof. Among Examples 1 to 4, Examples 1 to 3 are examples, and Example 4 is a comparative example.

[0287] Hereinafter, CF3CF2CF2OCF(CF3)CF2OCF(CF3)C(=O)F will be denoted as (HFPO)3.

[0288] <Example 1>

[0289] (Inner surface fluorination operation)

[0290] After blowing nitrogen gas into a 500 mL autoclave made of SUS316 for 1 hour, the pressure in the autoclave was increased to 0.100 MPa with fluorine gas diluted to 20 vol% with nitrogen gas (also denoted as "20 vol% fluorine gas") and maintained for 5 hours, thereby performing an inner surface fluorination operation, and it was used as a reactor.

[0291] Thereafter, the 20 vol% fluorine gas in the reactor was taken out and nitrogen gas was blown in for 2 hours.

[0292] (Preparation of raw material solution)

[0293] On the other hand, 10 g of CH3CH2OCH2CH2OCH2CH2OCOCF(CF3)OCF2CF(CF3)OCF2CF2CF3 as a raw material compound was dissolved in 240 g of (HFPO)3 to obtain a raw material solution.

[0294] CH3CH2OCH2CH2OCH2CH2OCOCF(CF3)OCF2CF(CF3)OCF2CF2CF3 was prepared according to Example 1 (Step 1-1) of International Publication No. 2008 / 026707. (HFPO)3 was a product manufactured by AGC Inc.

[0295] (Fluorination operation of raw material compound)

[0296] 200 g of (HFPO)3 was added to the autoclave that had undergone the above inner surface fluorination operation and stirred, and nitrogen gas was blown in for 1 hour. Thereafter, 20 vol% fluorine gas was blown in at a flow rate of 5.66 L / hour for 1 hour, and while maintaining the same flow rate, the raw material solution was injected over 5 hours.

[0297] Next, while maintaining the above flow rate, 20% by volume of fluorine gas was blown in, and 20 mL of a (HFPO)3 solution of benzene (0.01 g / mL) was injected, followed by stirring for 1 hour.

[0298] Thereafter, nitrogen gas was blown in for 2 hours, and the resulting crude liquid was concentrated using an evaporator. 19 F-NMR and 1 H-NMR were used to quantify the product. The fluorination rate determined by the above method was 88%.

[0299] <Example 2>

[0300] A 500 mL high-pressure autoclave made of Ni was used instead of the SUS316 high-pressure autoclave, and the procedure was otherwise the same as in Example 1.

[0301] When 19 F-NMR was used to quantify the product, the fluorination rate was 89%.

[0302] <Example 3>

[0303] A 500 mL SUS316 high-pressure autoclave lined with PFA resin was used instead of the SUS316 high-pressure autoclave, and the inner surface fluorination operation was not performed. Otherwise, the procedure was the same as in Example 1.

[0304] When 19 F-NMR was used to quantify the product, the fluorination rate was 87%.

[0305] <Example 4>

[0306] A 500 mL SUS316 high-pressure autoclave was used for the test without performing the inner surface fluorination operation. Otherwise, the procedure was the same as in Example 1.

[0307] When 19 F-NMR was used to quantify the product, the fluorination rate was 75%.

[0308] <Measurement of pressure change>

[0309] To confirm whether the inner surface of the reactor in each example was inert to fluorine gas, the following operation was carried out to measure the pressure change.

[0310] Specifically, after the test of each example was carried out, to determine the state of the reactor, nitrogen gas was blown into each high-pressure autoclave for 1 hour, and then the pressure was increased to 0.100 MPa inside the high-pressure autoclave using 20% by volume of fluorine gas and maintained for 5 hours, and the pressure change was measured.

[0311] A pressure change of 0.001 MPa or less was evaluated as A, and a pressure change exceeding 0.001 MPa was evaluated as B. The results are shown in Table 1.

[0312] <Evaluation of corrosion resistance>

[0313] In each case, the fluorination operation of the aforementioned raw material compound was repeatedly carried out until the total flow of 20% by volume of fluorine gas exceeded 72 hours. The wall thickness of the reactor before and after the operation was measured, and the rate of thickness reduction per year (unit: mm / year) was calculated based on the difference.

[0314] A case where the rate of thickness reduction was less than 0.1 mm / year was evaluated as A, and a case where it was 0.1 mm / year or more was evaluated as B. The results are shown in Table 1.

[0315] The materials of the reactor main body, the components contained in the surface layer of the inner surface of the reactor, and the fluorination rate in Examples 1 to 4 are shown together in Table 1. In the table, "-" indicates that no surface layer was provided on the inner surface of the reactor.

[0316] [Table 1]

[0317] Example 1 Example 2 Example 3 Example 4 Material of the reactor main body SUS 316 Ni SUS 316 SUS 316 Composition of the reactor surface layer Metal fluoride Metal fluoride PFA - Amount of pressure change A A A B Corrosion resistance A A A B Fluorination rate (%) 88 89 87 75

[0318] As shown in Table 1, Examples 1 to 3 had a higher fluorination rate compared to Example 4. Examples 1 to 3 had higher corrosion resistance of the reactor compared to Example 4, and thus it can be considered that a high fluorination rate can be obtained.

[0319] Industrial applicability

[0320] The method for producing a fluorine-containing compound of the present application can produce a fluorine-containing compound with a high fluorination rate. The obtained fluorine-containing compound can be derived 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 fluorine-containing compounds that can be derived from the fluorine-containing compound can be used in surface treatment agents, emulsifiers, rubbers, surfactants, solvents, heat media, pharmaceuticals, pesticides, lubricating oils, and their intermediates, etc.

[0321] The entire disclosure of Japanese Patent Application No. 2022-185979 filed on November 21, 2022 is incorporated herein by reference. All documents, patent applications, and technical standards described in this specification are incorporated herein by reference to the same extent as when each individual document, patent application, and technical standard is specifically and separately incorporated by reference.

Claims

1. A method for manufacturing a fluorine-containing compound, comprising: Inside a reactor having an inner surface that is inactive to fluorine gas, a gas containing fluorine gas is introduced into a composition containing an organic compound having at least one fluorinable atom, thereby fluorinating the organic compound.

2. The method for producing a fluorine-containing compound according to claim 1, wherein, When the reactor is filled with a mixed gas containing 20% by volume of fluorine gas and 80% by volume of nitrogen gas at a pressure of 0.100 MPa and held for 5 hours, the difference between the pressure at the time of filling and the pressure after holding is 0.001 MPa or less.

3. The method for producing a fluorine-containing compound according to claim 1, wherein, The inner surface that is inactive to fluorine gas contains a metal fluoride.

4. The method for producing a fluorine-containing compound according to claim 3, wherein, The reactor is a container in which the inner surface is made inactive to fluorine gas by filling and holding a gas containing fluorine gas inside a container having a metal element on the inner surface.

5. The method for producing a fluorine-containing compound according to claim 1, wherein, The inner surface that is inactive to fluorine gas contains a fluororesin.

6. The method for producing a fluorine-containing compound according to claim 1, wherein, The reactor has a reactor body and a surface layer. The reactor body contains at least one element selected from the group consisting of nickel, copper, aluminum, chromium, iron, silver, titanium, and molybdenum, and the surface layer is located on the inner surface of the reactor body and is inactive to fluorine gas.

7. The method for producing a fluorine-containing compound according to any one of claims 1 to 6, wherein, The composition is a liquid at 25°C at the temperature at which the fluorination is carried out.

8. The method for producing a fluorine-containing compound according to any one of claims 1 to 6, wherein, The organic compound has a divalent or higher functional group containing at least one of an oxygen atom and a sulfur atom.

9. The method for producing a fluorine-containing compound according to any one of claims 1 to 6, wherein, The organic compound has 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.

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