Method for producing fluorine-containing compounds

Abstract

This method for producing fluorine-containing compounds comprises introducing, in a reactor having an inner surface inert to fluorine gas, a gas containing fluorine gas into a composition containing an organic compound having at least one atom capable of being fluorinated, and thereby fluorinating the organic compound.

Description

Method for producing fluorine-containing compounds

[0001] The present disclosure relates to a method for producing a fluorine-containing compound.

[0002] As a method for fluorinating an organic compound having at least one fluorinatable atom, a method of direct fluorination with fluorine gas is known (for example, Patent Document 1). In direct fluorination with fluorine gas, for example, a gas containing fluorine gas is introduced into a composition containing the organic compound inside a reactor. This causes the organic compound to react with the fluorine gas, and the fluorinatable atom in the organic compound is replaced with a fluorine atom.

[0003] WO 2000 / 056694

[0004] As a reactor used for direct fluorination with fluorine gas, a container made of a metal such as nickel is usually used. However, when direct fluorination with fluorine gas is carried out inside the reactor, the fluorine gas introduced to fluorinate an organic compound may react with the inner surface of the reactor. When the fluorine gas reacts with the inner surface of the reactor, the reactor is corroded and the fluorine gas is consumed, so that the amount of fluorine gas used for fluorination of an organic compound decreases, and the fluorination rate may decrease.

[0005] An object of one embodiment of the present invention is to provide a method for producing a fluorine-containing compound with a high fluorination rate in direct fluorination with fluorine gas inside a reactor.

[0006] The present disclosure includes the following aspects. <1> A method for producing a fluorine-containing compound, comprising introducing a gas containing fluorine gas into a composition containing an organic compound having at least one fluorinatable atom inside a reactor having an inner surface inert to fluorine gas, thereby fluorinating the organic compound. <2> The method for producing a fluorine-containing compound according to <1>, wherein, when the reactor is filled with a mixed gas containing 20 volume % fluorine gas and 80 volume % 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. <3> The method for producing a fluorine-containing compound according to <1> or <2>, wherein the inner surface inert to fluorine gas contains a metal fluoride. <4> The method for producing a fluorine-containing compound according to <3>, wherein the reactor is a container having a metal element on the inner surface, the inner surface of which is made inert to fluorine gas by filling and maintaining a gas containing fluorine gas inside the container. <5> The method for producing a fluorine-containing compound according to <1> or <2>, wherein the inner surface inert to fluorine gas contains a fluororesin. <6> The method for producing a fluorine-containing compound according to any one of <1> to <5>, wherein the reactor has a reactor body containing at least one element selected from the group consisting of nickel, copper, aluminum, chromium, iron, silver, titanium, and molybdenum, and a surface layer inert to fluorine gas located on the inner surface of the reactor body. <7> The method for producing a fluorine-containing compound according to any one of <1> to <6>, wherein the composition is liquid at the temperature at which the fluorination is carried out. <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. <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 bond 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.

[0007] According to the present disclosure, there is provided a method for producing a fluorine-containing compound with a high fluorination rate in direct fluorination with fluorine gas inside a reactor.

[0008] Hereinafter, modes for carrying out embodiments of the present disclosure will be described in detail. However, the embodiments of the present disclosure are not limited to the following embodiments. In the following embodiments, components (including element steps, etc.) are not essential unless otherwise specified. The same applies to numerical values ​​and their ranges, and they do not limit the embodiments of the present disclosure.

[0009] In the present disclosure, a numerical range indicated using "to" means a range that includes the numerical values ​​before and after "to" as the minimum and maximum values, respectively. In the numerical ranges described in stages in the present disclosure, the upper or lower limit value described in a certain numerical range may be replaced with the upper or lower limit value of another numerical range described in stages. Furthermore, in the numerical ranges described in the present disclosure, the upper or lower limit value described in a certain numerical range may be replaced with a value shown in the Examples. In the present disclosure, a combination of two or more preferred embodiments is a more preferred embodiment. In the present disclosure, when multiple substances corresponding to each component are present, the amount of each component refers to the total amount of multiple substances unless otherwise specified. In the present disclosure, when a compound is represented by a specific formula (X), the compound represented by the formula (X) may be referred to as compound (X).

[0010] [Method for producing a fluorine-containing compound] A method for producing a fluorine-containing compound according to one embodiment of the present disclosure comprises introducing a gas containing fluorine gas into a composition containing an organic compound having at least one fluorinatable atom in a reactor having an inner surface inert to fluorine gas, thereby fluorinating the organic compound. Hereinafter, the organic compound having at least one fluorinatable atom is also referred to as a "raw material compound."

[0011] As described above, when direct fluorination with fluorine gas is carried out inside a metal reactor, the fluorine gas may react with the inner surface of the reactor. When the fluorine gas reacts with the inner surface of the reactor, the reactor may corrode and the fluorine gas may be consumed in the reaction with the inner surface of the reactor, resulting in a low fluorination rate. In contrast, in the above-mentioned production method, direct fluorination with fluorine gas is carried out inside a reactor having an inner surface that is inert to fluorine gas. Therefore, corrosion of the reactor is suppressed and the consumption of fluorine gas due to the reaction with the inner surface of the reactor is also suppressed, resulting in a high fluorination rate.

[0012] Here, whether or not a reactor for carrying out direct fluorination with fluorine gas is a "reactor having an inner surface inert to fluorine gas" can be confirmed as follows. Specifically, first, nitrogen gas is blown into the reactor to be confirmed for 1 hour, and then 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. If the difference between the pressure at the time of filling with the mixed gas, i.e., 0.100 MPa, and the pressure after maintaining the pressure for 5 hours is 0.001 MPa or less, the inner surface of the reactor is inert to fluorine gas. Hereinafter, the difference between the pressure at the time of filling with the mixed gas and the pressure after maintaining the pressure for 5 hours will also be referred to as the "pressure change amount."

[0013] A pressure change of 0.001 MPa or less means that fluorine gas is not consumed during the 5-hour holding period. In other words, it means that the inner surface of the reactor is inert to fluorine gas. On the other hand, if the pressure after 5 hours of holding decreases from the pressure at the time of filling the mixed gas and the pressure change exceeds 0.001 MPa, it is considered that fluorine gas reacts with components on the inner surface of the reactor during the 5-hour holding period, and the fluorine gas is consumed. In other words, it is considered that the inner surface of the reactor is not inert to fluorine gas.

[0014] <Reactor> The reactor having an inner surface inert to fluorine gas is not particularly limited as long as the inner surface is inert to fluorine gas, and examples thereof include a reactor containing a metal fluoride on the inner surface and a reactor containing a fluororesin on the inner surface. The reactor may have a reactor body and a surface layer inert to fluorine gas, which is located on the inner surface of the reactor body. The reactor having an inner surface inert 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.

[0015] The material of the reactor body is not particularly limited, but metal is preferred from the viewpoint of enabling operation under a wide range of temperature and pressure conditions. The material of the reactor body may be a pure metal consisting of a single metal element, or an alloy containing two or more elements. 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, in a reactor body containing at least one element selected from the group consisting of nickel, copper, aluminum, chromium, iron, silver, titanium, and molybdenum, when fluorine gas directly contacts the inner surface, the inner surface of the reactor body is likely to react with the fluorine gas. In contrast, by providing a surface layer inert 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 can be suppressed. From the viewpoints of availability and economy, nickel and stainless steel are preferred as the material of the reactor body.

[0016] (Reactor containing metal fluoride on the inner surface) A reactor containing metal fluoride on the inner surface can be obtained, for example, by carrying out an operation of filling and maintaining a gas containing fluorine gas inside a container containing a metal element on the inner surface. Hereinafter, the operation of filling and maintaining a gas containing fluorine gas inside a container will also be referred to as an "internal fluorination operation". The container that has undergone the above internal fluorination operation has an inner surface that is inert to fluorine gas by being fluorinated. This container is used as a reactor. An example of a reactor that is a container that has undergone the above internal fluorination operation is a reactor having a reactor main body and a surface layer that is located on the inner surface of the reactor main body and contains a metal fluoride and is inert to fluorine gas.

[0017] The conditions for the internal fluorination operation are not particularly limited as long as the conditions are such that the inner surface of the resulting reactor is inert to fluorine gas. The gas used in the internal fluorination operation only needs to contain at least fluorine gas. The gas may consist of fluorine gas or may contain a gas other than fluorine gas. Examples of gases other than fluorine gas include inert gases. Examples of inert gases include nitrogen gas, helium gas, neon gas, argon gas, etc., with nitrogen gas or helium gas being preferred, and nitrogen gas being preferred from the viewpoint of keeping costs low. From the viewpoint of obtaining a reactor having an inner surface inert to fluorine gas, the concentration of fluorine gas in the gas used in the internal fluorination operation is preferably 10% by volume or more, more preferably 15% by volume or more, and even more preferably 20% by volume or more. From the viewpoint of excellent safety, the concentration of fluorine gas in the gas used in the internal fluorination operation is preferably 60% by volume or less, more preferably 50% by volume or less, and even more preferably 40% by volume or less. From the above viewpoint, the concentration of fluorine gas in the gas used in the internal fluorination operation is preferably 10 to 60% by volume, more preferably 15 to 50% by volume, and even more preferably 20 to 40% by volume.

[0018] The pressure at the time of filling the gas in the internal fluorination operation is preferably 0.001 MPa or more, more preferably 0.010 MPa or more, from the viewpoint of obtaining a reactor having an inner surface inert to fluorine gas. The pressure at the time of filling the gas in the internal fluorination operation is preferably 1.000 MPa or less, more preferably 0.200 MPa or less, from the viewpoint of excellent safety. From the above viewpoint, the pressure at the time of filling the gas in the internal fluorination operation is preferably 0.001 to 1.000 MPa, more preferably 0.010 to 0.200 MPa. The retention time of the gas in the internal fluorination operation is preferably 30 minutes or more, more preferably 1 hour or more, from the viewpoint of obtaining a reactor having an inner surface inert to fluorine gas. The upper limit of the retention time of the gas in the internal fluorination operation is not particularly limited. The retention time of the gas in the internal fluorination operation may be 72 hours or less, 50 hours or less, or 10 hours or less. The gas retention time in the internal fluorination operation is preferably 30 minutes to 72 hours, more preferably 1 hour to 50 hours, and even more preferably 1 hour to 10 hours.

[0019] The "container containing a metal element on its inner surface" before the internal fluorination operation may be a container that is the reactor body itself, or a container with a surface layer formed on the inner surface of the reactor body. The surface layer may be a layer made of the same material as the reactor body, or a layer made of a different material from the reactor body. Examples of the surface layer include a layer of a metal element alone that is not contained in the reactor body, and a layer of an alloy containing a metal element that is not contained in the reactor body. Specific examples of the material for the surface layer include nickel, titanium, etc.

[0020] When the inner surface fluorination operation is performed on the vessel which is the reactor body itself, a part of the inner surface of the reactor body is fluorinated to form a surface layer which contains a metal fluoride and is inactive to fluorine gas. Therefore, the surface layer which is inactive to fluorine gas contains a metal fluoride which is a fluorinated metal element contained in the reactor body.

[0021] On the other hand, when an internal fluorination operation is performed on a vessel having a surface layer formed on the inner surface of the reactor body, at least a part of the surface layer is fluorinated to become a surface layer containing a metal fluoride and inactive to fluorine gas. Therefore, the surface layer inactive to fluorine gas contains a metal fluoride obtained by fluorinating the metal element contained in the surface layer before the internal fluorination operation. In other words, the metal fluoride contained in the surface layer inactive to fluorine gas may be the same metal element as the metal element contained in the reactor body, or may be the fluorinated metal element of a different metal element.

[0022] Examples of metal fluorides include fluorides of at least one element selected from the group consisting of nickel, copper, aluminum, chromium, iron, silver, titanium, and molybdenum. Surface layers containing metal fluorides, which are fluorides of these metal elements, may peel off, for example, when exposed to moisture in the air. Therefore, when fluorinating a raw material compound using a reactor containing a metal fluoride on its inner surface, it is preferable to fluorinate the raw material compound after the internal fluorination operation without contacting a moisture-containing gas with the inner surface of the reactor. For example, it is preferable to perform the internal fluorination operation and the fluorination of the raw material compound as a series of operations.

[0023] (Reactor containing fluororesin on the inner surface) A reactor containing fluororesin on the inner surface can be obtained, for example, by forming a surface layer containing fluororesin on the inner surface of a reactor body. That is, a reactor having a reactor body and a surface layer located on the inner surface of the reactor body, containing fluororesin and inert to fluorine gas, can be obtained. Examples of the reactor body include the same as the reactor body in the above-mentioned reactor containing a metal fluoride on the inner surface.

[0024] Examples of the fluororesin include tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), polytetrafluoroethylene (PTFE), etc. The method for forming a surface layer containing a fluororesin on the inner surface of the reactor body is not particularly limited, and examples thereof include hot molding of the fluororesin.

[0025] <Composition> The composition to be introduced into a reactor having an inner surface inert to fluorine gas is not particularly limited as long as it contains a raw material compound, and may be in the form of a liquid, gas, or solid at the temperature at which the raw material compound is fluorinated. From the viewpoint of improving the yield of the fluorine-containing compound, the composition is preferably a liquid at the temperature at which the raw material compound is fluorinated. The composition contains at least a raw material compound that is an organic compound having at least one fluorinatable atom, and may further contain a solvent, other additives, etc., as necessary.

[0026] (Raw Material Compound) The raw material compound is not particularly limited as long as it is an organic compound having at least one fluorinable atom. Examples of the fluorinable atom include a hydrogen atom, a bromine atom, and an iodine atom. The raw material compound may have only one fluorinable atom, or may have two or more fluorinable atoms. The number of fluorinable atoms contained in one molecule of the raw material compound is, for example, 1 to 1,000, preferably 1 to 500, and more preferably 1 to 100.

[0027] The raw material 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, the 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."

[0028] 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. Examples of the specific functional group include an ester bond, an ether bond, an amide bond, a thioether bond, a thioester bond, and a sulfonyl group. Examples of the specific functional group include carbonyl groups other than ester bonds and amide bonds, and imide bonds. The raw material compound is preferably a compound having at least one specific functional group 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, more preferably a compound having at least one of an ester bond and an ether bond, even more preferably a compound having an ester bond, and particularly preferably a compound having both an ester bond and an ether bond.

[0029] In particular, when a raw material compound has an ester bond and a fluorinable atom is bonded to a carbon atom bonded to the oxygen atom of the ester bond, the fluorinable atom is less likely to be fluorinated. On the other hand, in this embodiment, the fluorination reaction is carried out inside a reactor having an inner surface inert to fluorine gas. Therefore, even when a raw material compound is used that has an ester bond and a fluorinable atom is bonded to a carbon atom bonded to the oxygen atom of the ester bond, a high fluorination rate can be obtained in direct fluorination with fluorine gas. In other words, the raw material compound may be a compound that has an ester bond as a specific functional group and a fluorinable atom is bonded to a carbon atom bonded to the oxygen atom of the ester bond. Alternatively, the raw material compound may be a compound that has an ester bond and an ether bond as specific functional groups and a fluorinable atom is bonded to a carbon atom bonded to the oxygen atom of the ester bond.

[0030] The number average molecular weight of the raw material compound is not particularly limited, and may be, for example, 100 to 100,000. From the viewpoint of excellent solubility in a solvent described later, it is preferably 100 to 20,000, more preferably 300 to 10,000, and even more preferably 400 to 6,000. The number average molecular weight of the raw material compound is１ H-NMR and １９ It is the number average molecular weight of each molecule calculated from the molecular structure identified by F-NMR.

[0031] Examples of the raw material compound include a compound represented by the following formula (1) and a compound represented by the following formula (2). Ａ１ -O-(C=O)-R Ｂ１ …(1) R Ｂ２ -(C=O)-OR Ａ２ -O-(C=O)-R Ｂ３ …(2)

[0032] In formulas (1) and (2), R Ａ１ , R Ｂ１ , R Ｂ２ , and R Ｂ３ are each independently a monovalent saturated hydrocarbon group, a halogeno monovalent saturated hydrocarbon group, a heteroatom-containing monovalent saturated hydrocarbon group, or a halogeno (heteroatom-containing monovalent saturated hydrocarbon) group; R Ａ２ is a divalent saturated hydrocarbon group, a halogeno divalent saturated hydrocarbon group, a heteroatom-containing divalent saturated hydrocarbon group, or a halogeno (heteroatom-containing divalent saturated hydrocarbon) group.

[0033] In the present disclosure, the "monovalent saturated hydrocarbon group" may be any of a linear alkyl group, a branched alkyl group, and a cycloalkyl group. The "divalent saturated hydrocarbon group" may be any of a linear alkylene group, a branched alkylene group, and a cycloalkylene group. The linear alkyl group, branched alkyl group, linear alkylene group, and branched alkylene group may contain an alicyclic structure.

[0034] In the present disclosure, the term "halogeno" means that one or more hydrogen atoms present in a group are substituted with at least one halogen atom selected from a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Hydrogen atoms may or may not be present in the group.

[0035] In the present disclosure, the term "halogeno monovalent saturated hydrocarbon group" refers to a group in which one or more hydrogen atoms present in a monovalent saturated hydrocarbon group have been substituted with a halogen atom. The term "halogeno divalent saturated hydrocarbon group" refers to a group in which one or more hydrogen atoms present in a divalent saturated hydrocarbon group have been substituted with a halogen atom.

[0036] In the present disclosure, "heteroatom" means an atom other than carbon or hydrogen atoms, and includes, for example, nitrogen, oxygen, and sulfur atoms.

[0037] In the present disclosure, the term "heteroatom-containing monovalent saturated hydrocarbon group" refers to a monovalent saturated hydrocarbon group that contains a divalent heteroatom or a divalent group containing a heteroatom. The term "heteroatom-containing divalent saturated hydrocarbon group" refers to a divalent saturated hydrocarbon group that contains a divalent heteroatom or a divalent group containing a heteroatom. Examples of divalent heteroatoms include -O- and -S-. Furthermore, examples of divalent groups containing heteroatoms include -NH-, -C(=O)-, and -SO. ２ - are listed.

[0038] In this disclosure, the term "halogeno (heteroatom-containing monovalent saturated hydrocarbon) group" refers to a group in which one or more hydrogen atoms in the above heteroatom-containing monovalent saturated hydrocarbon group have been substituted with halogen atoms. The term "halogeno (heteroatom-containing divalent saturated hydrocarbon group) group" refers to a group in which one or more hydrogen atoms in the above heteroatom-containing divalent saturated hydrocarbon group have been substituted with halogen atoms.

[0039] In formula (1), R Ａ１ and R Ｂ１ Preferably, at least one of R Ａ２ , R Ｂ２ , and R Ｂ３ It is preferred that at least one selected from the group consisting of contains a hydrogen atom.

[0040] [R Ａ１ ] In formula (1), R Ａ１is a monovalent saturated hydrocarbon group, a halogeno monovalent saturated hydrocarbon group, a heteroatom-containing monovalent saturated hydrocarbon group, or a halogeno(heteroatom-containing monovalent saturated hydrocarbon) group.

[0041] R Ａ１ Examples of the monovalent saturated hydrocarbon group represented by the formula (I) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group, a 2-ethylhexyl group, and a cyclohexyl group.

[0042] R Ａ１ The halogeno monovalent saturated hydrocarbon group represented by the following formula is preferably a halogenoalkyl group: The halogen atom contained in the halogeno monovalent saturated hydrocarbon group is preferably a fluorine atom, a chlorine atom, or a bromine atom, and more preferably a fluorine atom.

[0043] R Ａ１ The heteroatom-containing monovalent saturated hydrocarbon group represented by the formula (I) is preferably a monovalent saturated hydrocarbon group containing an ethereal oxygen atom (that is, —O—), and more preferably an alkyl group containing an ethereal oxygen atom.

[0044] R Ａ１ The halogeno (heteroatom-containing monovalent saturated hydrocarbon) group represented by the formula (I) is preferably a halogeno (heteroatom-containing alkyl group). The halogen atom contained in the halogeno (heteroatom-containing monovalent saturated hydrocarbon) group is preferably a fluorine atom, a chlorine atom, or a bromine atom. The halogeno (heteroatom-containing monovalent saturated hydrocarbon) group is preferably a halogeno monovalent saturated hydrocarbon group containing an ethereal oxygen atom, and more preferably a halogenoalkyl group containing an ethereal oxygen atom.

[0045] R Ａ１ The number of carbon atoms is preferably 1 to 200, more preferably 3 to 100, from the viewpoint of excellent solubility in a solvent described later.

[0046] Among these, from the viewpoint of excellent solubility in solvents described later, R Ａ１ is preferably represented by the following formula (A1): Ａ１R 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. １１ O-(R １２ O) ｍ１ -R １３ - ... (A1)

[0047] In formula (A1), R １１ is an alkyl group which may have a fluorine atom, and R １２ are each independently an alkylene group having 1 to 6 carbon atoms which may have a fluorine atom, and R １３ represents an alkylene group having 1 to 6 carbon atoms which may have a fluorine atom, and m1 represents an integer of 0 to 500.

[0048] In formula (A1), R １１ Examples of the alkyl group include alkyl groups and fluoroalkyl groups.

[0049] R １１ The number of carbon atoms of is preferably 1 to 100, more preferably 1 to 50, even more preferably 1 to 10, and particularly preferably 1 to 6, from the viewpoint of excellent solubility in a solvent described later.

[0050] R １１ The alkyl group represented by the formula (I) may be a linear alkyl group, a branched alkyl group, or an alkyl group having a ring structure.

[0051] R １１ The fluoroalkyl group represented by the formula (I) may be a straight-chain fluoroalkyl group, a branched-chain fluoroalkyl group, or a fluoroalkyl group having a ring structure.

[0052] Among them, R １１ is preferably an alkyl group, more preferably a linear alkyl group, and even more preferably a linear alkyl group having 1 to 6 carbon atoms.

[0053] In formula (A1), -(R １２ O) ｍ１ - is preferably represented by the following formula (A2): -[(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) However, R ｆ１ is an alkylene group having 1 carbon atom which may have a fluorine atom, and R ｆ２ is an alkylene group having 2 carbon atoms which may have a fluorine atom, and R ｆ３ is an alkylene group having 3 carbon atoms which may have a fluorine atom, and R ｆ４ is an alkylene group having 4 carbon atoms which may have a fluorine atom, and R ｆ５ is an alkylene group having 5 carbon atoms which may have a fluorine atom, and R ｆ６ represents an alkylene group having 6 carbon atoms which may have a fluorine atom. k1, k2, k3, k4, k5, and k6 each independently represent an integer of 0 or 1 or more, and k1+k2+k3+k4+k5+k6 is an integer of 0 to 500.

[0054] From the viewpoint of excellent solubility in a solvent 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.

[0055] In addition, (R ｆ１ O) ~ (R ｆ６ O) may be bonded in any order. k1 to k6 in formula (A2) are each ｆ１ O) ~ (R ｆ６ O), and does not represent the arrangement. For example, (R ｆ５ O) ｋ５ is (R ｆ５ O) is k5, and (R ｆ５ O) ｋ５ Similarly, (R ｆ１ O) ~ (R ｆ６ The order of description of each unit does not represent the bonding order of the units.

[0056] R ｆ３ ~R ｆ６ In the formula (I), the alkylene group which may have a fluorine atom may be a linear alkylene group, a branched alkylene group, or an alkylene group having a ring structure.

[0057] R ｆ１ Specific examples of the group include -CH ２ -, -CF ２ - and -CHF-.

[0058] R ｆ２ Specific examples of the group include -CH ２ CH ２ -, -CF ２ CF ２ -, -CF ２ CHF-, -CHFCF ２ -, -CHFCHF-, -CH ２ CF ２ - and -CH ２ Examples include CHF-.

[0059] R ｆ３ Specific examples of the group include -CH ２ CH ２ CH ２ -, -CF ２ CF ２ CF ２ -, -CF ２ CHFCF ２ -, -CF ２ CH ２ CF ２ -, -CHFCF ２ CF ２ -, -CHFCHFCF ２ -, -CHFCHFCHF-, -CHFCH ２ CF ２ -, -CH ２ CF ２ CF ２ -, -CH ２ CHFCF ２ -, -CH ２ CH ２ CF ２ -, -CH ２ CF ２ CHF-, -CH ２ CHFCHF-, -CH ２CH ２ CHF−, −CF(CF ３ )−CF ２ −, −CF(CHF ２ )−CF ２ −, −CF(CH ２ F)−CF ２ −, −CF(CH ３ )−CF ２ −, −CF(CF ３ )−CHF−, −CF(CHF ２ )−CHF−, −CF(CH ２ F)−CHF−, −CF(CH ３ )−CHF−, −CF(CF ３ )−CH ２ −, −CF(CHF ２ )−CH ２ −, −CF(CH ２ F)−CH ２ −, −CF(CH ３ )−CH ２ −, −CH(CF ３ )−CF ２ −, −CH (CHF ２ )−CF ２ −, −CH(CH ２ F)−CF ２ −, −CH(CH ３ )−CF ２ −, −CH(CF ３ )−CHF−, −CH(CHF ２ )−CHF−, −CH(CH ２ F)−CHF−, −CH(CH ３ )−CHF−, −CH(CF ３ )−CH ２ −, −CH(CHF ２ )−CH ２ −, and −CH(CH ２ F)−CH ２ − are included.

[0060] R ｆ４ Specific examples of −CH ２ CH ２ CH ２ CH ２ −, −CF ２ CF ２ CF ２ CF ２ −, −CF２ CF ２ CF ２ CHF-、-CF ２ CF ２ CF ２ CH ２ -、-CF ２ CHFCF ２ CF ２ -、-CHFCHFCF ２ CF ２ -、-CH ２ CHFCF ２ CF ２ -、-CF ２ CH ２ CF ２ CF ２ -、-CHFCH ２ CF ２ CF ２ -、-CH ２ CH ２ CF ２ CF ２ -、-CHFCF ２ CHFCF ２ -、-CH ２ CF ２ CHFCF ２ -、-CF ２ CHFCHFCF ２ -、-CHFCHFCHFCF ２ -、-CH ２ CHFCHFCF ２ -、-CF ２ CH ２ CHFCF ２ -、-CHFCH ２ CHFCF ２ -、-CH ２ CH ２ CHFCF ２ -、-CF ２ CH ２ CH ２ CF ２ -、-CHFCH ２ CH ２ CF ２ -、-CH ２ CH ２ CH ２ CF ２ -、-CHFCH ２ CH ２ CHF-、-CH ２ CH２ CH ２ CHF−, and - cycloC ４ F ６ - are mentioned.

[0061] R ｆ５ Specific examples of ２ CH ２ CH ２ CH ２ CH ２ -,-CF ２ CF ２ CF ２ CF ２ CF ２ ] -,-CHFCF ２ CF ２ CF ２ CF ２ -,-CH ２ CHFCF ２ CF ２ CF ２ -,-CF ２ CHFCF[[ID=5A]] ２ CF ２ CF ２ -,-CHFCHFCF ２ CF ２ CF ２ -,-CF ２ CH ２ CF ２ CF ２ CF ２ -,-CHFCH ２ CF ２ CF ２ CF ２ -,-CH ２ CH ２ CF ２ CF ２ CF ２ -,-CF ２ CF ２ CHFCF ２ CF ２ -,-CHFCF ２ CHFCF ２ CF ２ -,-CH ２ CF ２ CHFCF ２ CF ２ -,-CH ２ CF ２ CF ２ CF ２CH ２ -, and -cycloC ５ F ８ - are listed.

[0062] R ｆ６ Specific examples of the group include -CH ２ CH ２ CH ２ CH ２ CH ２ CH ２ -, -CF ２ CF ２ CF ２ CF ２ CF ２ CF ２ -, -CF ２ CF ２ CHFCHFCF ２ CF ２ -, -CHFCF ２ CF ２ CF ２ CF ２ CF ２ -, -CHFCHFCHFCHFCHFCHF-, -CHFCF ２ CF ２ CF ２ CF ２ CH ２ -, -CH ２ CF ２ CF ２ CF ２ CF ２ CH ２ -, and -cycloC ６ F １０ Here, -cycloC ４ F ６ - means a perfluorocyclobutanediyl group, and a specific example thereof is a perfluorocyclobutane-1,2-diyl group. ５ F ８ - means a perfluorocyclopentanediyl group, and a specific example thereof is a perfluorocyclopentane-1,3-diyl group. ６ F １０ "-" means a perfluorocyclohexanediyl group, and a specific example thereof is a perfluorocyclohexane-1,4-diyl group.

[0063] Among them, -(R １２ O) ｍ１ - preferably includes at least one selected from the group consisting of structures represented by the following formulas (F1) to (F3), and more preferably includes a structure represented by formula (F2): -(R ｆ１ O) ｋ１ - (R ｆ２ O) ｋ２ -...(F1) -(R ｆ２ O) ｋ２ - (R ｆ４ O) ｋ４ -...(F2) -(R ｆ３ O) ｋ３ - (F3) where the symbols in formulas (F1) to (F3) are the same as those in formula (A2) above.

[0064] In formula (F1) and formula (F2), (R ｆ１ O) and (R ｆ２ O), (R ｆ２ O) and (R ｆ４ O) can be bonded in any order. For example, (R ｆ１ O) and (R ｆ２ O) may be alternately arranged, and (R ｆ１ O) and (R ｆ２ O) may be arranged in blocks or randomly. The same applies to formula (F2). In formula (F1), k1 is preferably 1 to 30, more preferably 1 to 20. Also, k2 is preferably 1 to 30, more preferably 1 to 20. In formula (F2), k2 is preferably 1 to 30, more preferably 1 to 20. Also, k4 is preferably 1 to 30, more preferably 1 to 20. In formula (F3), k3 is preferably 1 to 30, more preferably 1 to 20.

[0065] In formula (A1), R １３ As the above, R ｆ１ ~R ｆ６ The same can be mentioned.

[0066] Among them, R １３ is preferably an alkylene group having 1 to 4 carbon atoms which may have a fluorine atom.

[0067] R Ａ１Specific examples of the structure include the following: * represents the bonding site with —O—, n1 represents an integer of 0 to 60, and n2 represents an integer of 0 to 200.

[0068]

[0069] [R Ｂ１ ] In formula (1), R Ｂ１ is a monovalent saturated hydrocarbon group, a halogeno monovalent saturated hydrocarbon group, a heteroatom-containing monovalent saturated hydrocarbon group, or a halogeno(heteroatom-containing monovalent saturated hydrocarbon) group.

[0070] R Ｂ１ Examples of the monovalent saturated hydrocarbon group represented by the formula (I) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group, a 2-ethylhexyl group, and a cyclohexyl group.

[0071] R Ｂ１ A halogenoalkyl group is preferred as the halogeno monovalent saturated hydrocarbon group represented by the following formula: The halogen atom contained in the halogeno monovalent saturated hydrocarbon group is preferably a fluorine atom, a chlorine atom, or a bromine atom.

[0072] R Ｂ１ The heteroatom-containing monovalent saturated hydrocarbon group represented by the formula (I) is preferably a monovalent saturated hydrocarbon group containing an ethereal oxygen atom (i.e., —O—), and more preferably an alkyl group containing an ethereal oxygen atom. Ｂ１ It is preferable that the alkyl group further has an ether bond.

[0073] R Ｂ１ The halogeno (heteroatom-containing monovalent saturated hydrocarbon) group represented by the formula (I) is preferably a halogeno (heteroatom-containing alkyl group). The halogen atom contained in the halogeno (heteroatom-containing monovalent saturated hydrocarbon) group is preferably a fluorine atom, a chlorine atom, or a bromine atom. The halogeno (heteroatom-containing monovalent saturated hydrocarbon) group is preferably a halogeno monovalent saturated hydrocarbon group containing an ethereal oxygen atom, and more preferably a halogenoalkyl group containing an ethereal oxygen atom.

[0074] R Ｂ１The number of carbon atoms of is preferably 1 to 100, more preferably 2 to 50, and even more preferably 3 to 20, from the viewpoint of excellent solubility in a solvent described later.

[0075] R Ｂ１ In terms of excellent solubility in solvents described below, it is preferable that the compound contains at least one fluorine atom and does not contain a hydrogen atom.

[0076] Among these, from the viewpoint of excellent solubility in solvents described later, R Ｂ１ is preferably represented by the following formula (B1): ２１ O-(R ２２ O) ｍ２ -R ２３ - ... (B1)

[0077] In formula (B1), R ２１ is an alkyl group which may have a fluorine atom, and R ２２ are each independently an alkylene group having 1 to 6 carbon atoms which may have a fluorine atom, and R ２３ represents an alkylene group having 1 to 6 carbon atoms which may have a fluorine atom, and m2 represents an integer of 0 to 20.

[0078] In formula (B1), R ２１ Examples of the alkyl group include alkyl groups and fluoroalkyl groups.

[0079] R ２１ The number of carbon atoms of is preferably 1 to 50, more preferably 1 to 10, and even more preferably 1 to 6, from the viewpoint of excellent solubility in a solvent described later.

[0080] 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. ２１ The fluoroalkyl group represented by the formula (I) may be a straight-chain fluoroalkyl group, a branched-chain fluoroalkyl group, or a fluoroalkyl group having a ring structure.

[0081] Among them, R ２１is 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.

[0082] In formula (B1), -(R ２２ O) ｍ２ - is preferably represented by the above formula (A2).

[0083] 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.

[0084] In formula (B1), R ２３ As the above, R ｆ１ ~R ｆ６ The same can be mentioned.

[0085] Among them, R ２３ is preferably a fluoroalkylene group having 1 to 3 carbon atoms, more preferably a perfluoroalkylene group having 1 to 3 carbon atoms.

[0086] R Ｂ１ Specific examples of the structure include the following: * represents the bonding site with —O—(C═O)—.

[0087]

[0088] [R Ａ２ ] In formula (2), R Ａ２ is a divalent saturated hydrocarbon group, a halogeno divalent saturated hydrocarbon group, a heteroatom-containing divalent saturated hydrocarbon group, or a halogeno (heteroatom-containing divalent saturated hydrocarbon) group.

[0089] R Ａ２ The divalent saturated hydrocarbon group, halogeno divalent saturated hydrocarbon group, heteroatom-containing divalent saturated hydrocarbon group, or halogeno (heteroatom-containing divalent saturated hydrocarbon) group represented by the formula (1) includes R Ａ１ and groups in which one hydrogen atom or one halogen atom has been removed from a halogeno (heteroatom-containing monovalent saturated hydrocarbon) group.

[0090] RＡ２ The number of carbon atoms is preferably 1 to 200, more preferably 3 to 100, from the viewpoint of excellent solubility in a solvent described later.

[0091] Among these, from the viewpoint of excellent solubility in solvents described later, R Ａ２ is preferably represented by the following formula (A5): Ａ２ -R 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. ３１ O-(R ３２ O) ｍ５ -R ３３ - ... (A5)

[0092] In formula (A5), R ３１ and R ３３ are each independently an alkylene group having 1 to 6 carbon atoms which may have a fluorine atom, and R ３２ are each independently an alkylene group having 1 to 6 carbon atoms which may have a fluorine atom; and m5 is an integer of 0 to 500.

[0093] In formula (A5), R ３１ and R ３３ R in formula (A1) １３ In formula (A5), -(R ３２ O) ｍ５ - is -(R １２ O) ｍ１ - and the same as above.

[0094] R Ａ２ Specific examples of the structure include the following: * represents the bonding site with —O—, and n2 represents an integer of 0 to 200.

[0095]

[0096] [R Ｂ２ and R Ｂ３ ] In formula (2), R Ｂ２ and R Ｂ３are each independently a monovalent saturated hydrocarbon group, a halogeno monovalent saturated hydrocarbon group, a heteroatom-containing monovalent saturated hydrocarbon group, or a halogeno (heteroatom-containing monovalent saturated hydrocarbon) group.

[0097] R Ｂ２ or R Ｂ３ The monovalent saturated hydrocarbon group, halogeno monovalent saturated hydrocarbon group, heteroatom-containing monovalent saturated hydrocarbon group, or halogeno (heteroatom-containing monovalent saturated hydrocarbon) group represented by the formula (1) includes R Ｂ１ Examples of such a group include a monovalent saturated hydrocarbon group represented by the following formula:

[0098] Examples of the raw material compound include the following compound (T1).

[0099]

[0100] From the viewpoint of obtaining a high fluorination rate, the content of the raw material compound contained in the composition is preferably from 1 to 100 mass%, more preferably from 3 to 100 mass%, particularly preferably from 3 to 70 mass%, and extremely preferably from 3 to 50 mass%, based on the total mass of the composition.

[0101] (Solvent) The composition may contain a solvent as needed. The solvent is not particularly limited as long as it can dissolve the raw material compounds.

[0102] From the viewpoint of excellent solubility of the raw material compound and the fluorine-containing compound obtained by fluorinating the raw material 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 a chlorine-containing solvent, and more preferably contains a chlorine-containing solvent. The chlorine-containing solvent is a solvent containing chlorine atoms. The chlorine-containing solvent preferably contains fluorine atoms in addition to chlorine atoms.

[0103] Examples of chlorine-containing solvents include CClF ２ CCFCF ２ OCF ２ CClF ２ (CFE-419), CH ２ ClCHClCH ２ OCF ２CHFCl (HCFE-473), CF ２ ClCFClCHFOCF ２ CF ２ Cl (HCFE-428a, b), CFHClCFClCF ２ OCF ２ CF ２ Cl (HCFE-428c, d), CF ２ ClCHClCF ２ OCF ２ CF ２ Cl (HCFE-428e), 1,2,3,4-tetrachloroperfluorobutane (R-113), CF ２ Cl-CFCl-CFCl-O-CF ２ -CF ２ Cl (CFE-418), CClHFCClFCHFOCF ２ CClF ２ (HCFE-437a, b), CClF ２ CClHCHFOCF ２ CClF ２ (HCFE-437c), CClHFCClFCH ２ OCF ２ CClF ２ (HCFE-446a), CF ２ ClCCl ２ CF ２ OCF ２ CFHCl (HCFE-427a,b), CF ２ HClFCF ２ OCF ２ CF ２ Examples of fluorine-containing solvents other than chlorine-containing solvents include perfluoroalkanes (FC-72, etc.), perfluoroethers (FC-75, FC-77, etc.), perfluoropolyethers (trade names: Krytox, Fomblin, Galden, Demnum, etc.), inert fluids (trade name: Fluorinert), and perfluorocarboxylic acid fluorides.

[0104] The boiling point of the solvent is preferably 10 to 500 ° C, more preferably 30 to 250 ° C, and even more preferably 50 to 150 ° C, from the viewpoint of improving the yield of the fluorine-containing compound. The number of carbon atoms in the solvent is preferably 4 or more, more preferably 4 to 1,000, even more preferably 4 to 500, particularly preferably 4 to 100, and most preferably 4 to 50, 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, even more preferably 200 to 25,000, particularly preferably 200 to 10,000, and most preferably 200 to 1,000. When there is a molecular weight distribution, the molecular weight represents the weight average molecular weight (Mw). Mw is measured in terms of polystyrene equivalent by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as an eluent.

[0105] (Other Additives) The composition may contain other additives as needed. Examples of other additives include an auxiliary that promotes the fluorination of the raw material compounds. Examples of auxiliary agents include a C-H bond-containing compound and a carbon-carbon double bond-containing compound other than the raw material compounds. Examples of C-H bond-containing compounds include benzene and toluene. Examples of carbon-carbon double bond-containing compounds include hexafluoropropylene and hexafluorobutadiene. Of these, aromatic hydrocarbons such as benzene and toluene are preferred as auxiliary agents.

[0106] <Fluorination Reaction> The gas introduced into the composition may contain at least fluorine gas. The gas may consist of fluorine gas or may contain a gas other than fluorine gas. Examples of gases other than fluorine gas include inert gases. Examples of inert gases include nitrogen gas, helium gas, neon gas, and argon gas. Nitrogen gas or helium gas is preferred, and nitrogen gas is preferred from the viewpoint of keeping costs low.

[0107] From the viewpoint of obtaining a high fluorination rate, the content of fluorine gas in the entire gas is preferably 10% by volume or more, more preferably 15% by volume or more, and even more preferably 20% by volume or more. From the viewpoint of excellent safety, the content of fluorine gas in the entire gas is preferably 60% by volume or less, more preferably 50% by volume or less, and even more preferably 40% by volume or less. From the above viewpoints, the content of fluorine gas in the entire gas is preferably 10 to 60% by volume, more preferably 15 to 50% by volume, and even more preferably 20 to 40% by volume.

[0108] The reaction temperature in the fluorination of the raw material compound is, for example, in the range of not less than −60° C. and not more than the boiling point of the raw material compound, and may be in the range of −50 to 100° C., or may be in the range of −20 to 50° C. The pressure in the fluorination of the raw material compound is, for example, 0 to 2 MPa. The fluorination of the raw material compound may be carried out by a batch method or a continuous method.

[0109] The residence time of a composition containing a raw material compound and into which fluorine gas has been introduced in a reactor in which the raw material compound is fluorinated is, from the viewpoint of increasing the fluorination rate, preferably 200 hours or less, more preferably 190 hours or less, even more preferably 170 hours or less, particularly preferably 150 hours or less, and extremely preferably 100 hours or less. Hereinafter, the residence time of the composition in the reactor will also be referred to as the "residence time." From the viewpoint of increasing the fluorination rate, the residence time is preferably 0.3 hours or more, more preferably 0.6 hours or more, even more preferably 1 hour or more, particularly preferably 2 hours or more, and extremely preferably 3 hours or more. The residence time is preferably 0.3 to 200 hours, more preferably 0.6 to 200 hours, even more preferably 1 to 200 hours, particularly preferably 1 to 190 hours, even more preferably 1 to 170 hours, extremely preferably 2 to 150 hours, and most preferably 3 to 100 hours. When the fluorination of the raw material compound is carried out in a continuous system, the residence time is calculated from the flow rate of the composition and the volume of the reactor. When the fluorination of the raw material compound is carried out in a continuous system, the residence time may be adjusted by the flow rate of the composition, the length of the reactor in the flow direction, etc.

[0110] The fluorination rate in the fluorination of the raw material compound is preferably 80% or more, more preferably 85% or more, even more preferably 87% or more, and particularly preferably 100%. The fluorination rate is determined as follows. Specifically, the reaction product is subjected to NMR measurement using an internal standard substance, and the fluorination rate is calculated by the following formula, assuming that the reaction product is a compound in which all fluorinatable atoms are completely fluorinated. Formula: Fluorination rate (%) = {1 - (number of fluorinatable atoms per molecule of reaction product) / (number of fluorinatable atoms per molecule of raw material compound)} × 100

[0111] <Fluorine-containing compound> The fluorine-containing compound obtained by fluorination of a raw material compound is a compound in which at least one of the fluorinatable atoms of the raw material compound is replaced with a fluorine atom. The fluorine-containing compound is preferably a compound in which all of the fluorinatable atoms of the raw material compound are replaced with fluorine atoms.

[0112] When the raw material compound is a compound represented by the formula (1), the fluorine-containing compound is preferably a compound represented by the following formula (3). When the raw material compound is a compound represented by the formula (2), the fluorine-containing compound is preferably a compound represented by the following formula (4). R ＡＦ１ -O-(C=O)-R ＢＦ１ …(3) R ＢＦ２ -(C=O)-OR ＡＦ２ -O-(C=O)-R ＢＦ３ ... (4) In formulas (6) and (7), R ＡＦ１ , R ＢＦ１ , R ＡＦ２ , R ＢＦ２ , and R ＢＦ３ are respectively R Ａ１ , R Ｂ１ , R Ａ２ , R Ｂ２ , and R Ｂ３ is a group corresponding to 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 , RＢＦ２ , and R ＢＦ３ is R Ａ１ , R Ｂ１ , R Ａ２ , R Ｂ２ , and R Ｂ３ is the same group as 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 is a group in which all hydrogen atoms present in are substituted with fluorine atoms.

[0113] [R ＡＦ１ ] In formula (3), R ＡＦ１ is R Ａ１ is a group corresponding to Ａ１ When contains a hydrogen atom, R ＡＦ１ is R Ａ１ R is a group in which all hydrogen atoms present in R have been substituted with fluorine atoms. Ａ１ When does not contain a hydrogen atom, R ＡＦ１ is R Ａ１ From the viewpoint of excellent solubility in solvents, R ＡＦ１ is preferably represented by the following formula (A3): １４ O-(R １５ O) ｍ３ -R １６ - ... (A3)

[0114] In formula (A3), R １４ is a perfluoroalkyl group, and R １５ are each independently a perfluoroalkylene group having 1 to 6 carbon atoms, and R １６ is a perfluoroalkylene group having 1 to 6 carbon atoms, and m3 is an integer of 0 to 500.

[0115] In formula (A3), R １４ is R in formula (A1).１１ Corresponds to R １１ When R contains a hydrogen atom, １４ is R １１ is a group in which all hydrogen atoms in R have been substituted with fluorine atoms. １１ When does not contain a hydrogen atom, R １４ is R １１ is the same as

[0116] In formula (A3), -(R １５ O) ｍ３ - represents -(R １２ O) ｍ１ Corresponds to -. R １２ When R contains a hydrogen atom, １５ is R １２ is a group in which all hydrogen atoms in R have been substituted with fluorine atoms. １２ When does not contain a hydrogen atom, R １５ is R １２ is the same as

[0117] In formula (A3), -(R １５ O) ｍ３ - is preferably represented by the following formula (A4): -[(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) However, R ｆｆ１ is a perfluoroalkylene group having one carbon atom, and R ｆｆ２ is a perfluoroalkylene group having 2 carbon atoms, R ｆｆ３ is a perfluoroalkylene group having 3 carbon atoms, R ｆｆ４ is a perfluoroalkylene group having 4 carbon atoms, R ｆｆ５ is a perfluoroalkylene group having 5 carbon atoms, R ｆｆ６is a perfluoroalkylene group having 6 carbon atoms. k7, k8, k9, k10, k11, and k12 each independently represent an integer of 0 or 1 or more, and k7 + k8 + k9 + k10 + k11 + k12 is an integer of 0 to 500.

[0118] In formula (A4), R ｆｆ１ ~R ｆｆ６ is R in formula (A2). ｆ１ ~R ｆ６ For example, R ｆ１ When R contains a hydrogen atom, ｆｆ１ is R ｆ１ is a group in which all hydrogen atoms in R have been substituted with fluorine atoms. ｆ１ When does not contain a hydrogen atom, R ｆｆ１ is R ｆ１ It is the same as R ｆｆ２ ~R ｆｆ６ Regarding R ｆｆ１ is the same as:

[0119] From the viewpoint of excellent solubility in solvents, 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.

[0120] Among them, -(R １５ O) ｍ３ - preferably includes at least one selected from the group consisting of structures represented by the following formulas (G1) to (G3), and more preferably includes a structure represented by formula (G2): -(R ｆｆ１ O) ｋ７ - (R ｆｆ２ O) ｋ８ -...(G1) -(R ｆｆ２ O) ｋ８ - (R ｆｆ４ O) ｋ１０ -...(G2) -(R ｆｆ３ O) ｋ９ − (G3) where the symbols in formulas (G1) to (G3) are the same as those in formula (A4) above.

[0121] In formula (G1) and formula (G2), (R ｆｆ１ O) and (R ｆｆ２ O), (Rｆｆ２ O) and (R ｆｆ４ O) can be bonded in any order. For example, (R ｆｆ１ O) and (R ｆｆ２ O) may be alternately arranged, and (R ｆｆ１ O) and (R ｆｆ２ O) may be arranged in blocks or randomly. The same applies to formula (G2). In formula (G1), k7 is preferably 1 to 30, more preferably 1 to 20. Also, k8 is preferably 1 to 30, more preferably 1 to 20. In formula (G2), k8 is preferably 1 to 30, more preferably 1 to 20. Also, k10 is preferably 1 to 30, more preferably 1 to 20. In formula (G3), k9 is preferably 1 to 30, more preferably 1 to 20.

[0122] In formula (A3), R １６ is R in formula (A1). １３ Corresponds to R １３ When R contains a hydrogen atom, １６ is R １３ is a group in which all hydrogen atoms in R have been substituted with fluorine atoms. １３ When does not contain a hydrogen atom, R １６ is R １３ is the same as

[0123] R １６ As the above, R ｆｆ１ ~R ｆｆ６ The same can be mentioned.

[0124] Among them, R １６ is preferably a perfluoroalkylene group having 1 to 3 carbon atoms.

[0125] In formula (A3), m3 corresponds to m1 in formula (A1). m3 is the same as m1.

[0126] R ＡＦ１ Specific examples of the structure include the following: * represents the bonding site with —O—, n1 represents an integer of 0 to 60, and n2 represents an integer of 0 to 200.

[0127]

[0128] [R ＢＦ１ ] In formula (3), RＢＦ１ is R Ｂ１ is a group corresponding to Ｂ１ When contains a hydrogen atom, R ＢＦ１ is R Ｂ１ R is a group in which all hydrogen atoms present in R have been substituted with fluorine atoms. Ｂ１ When does not contain a hydrogen atom, R ＢＦ１ is R Ｂ１ From the viewpoint of excellent solubility in solvents, R ＢＦ１ is preferably represented by the following formula (B2): ２４ O-(R ２５ O) ｍ４ -R ２６ - ... (B2)

[0129] In formula (B2), R ２４ is a perfluoroalkyl group, and R ２５ are each independently a perfluoroalkylene group having 1 to 6 carbon atoms, and R ２６ is a perfluoroalkylene group having 1 to 6 carbon atoms, and m4 is an integer of 0 to 20.

[0130] In formula (B2), R ２４ is R in formula (B1). ２１ Corresponds to R ２１ When R contains a hydrogen atom, ２４ is R ２１ is a group in which all hydrogen atoms in R have been substituted with fluorine atoms. ２１ When does not contain a hydrogen atom, R ２４ is R ２１ is the same as

[0131] In formula (B2), -(R ２５ O) ｍ４ - represents -(R ２２ O) ｍ２ Corresponds to -. R ２２ When R contains a hydrogen atom, ２５ is R ２２ is a group in which all hydrogen atoms in R have been substituted with fluorine atoms. ２２ When does not contain a hydrogen atom, R ２５ is R ２２ is the same as

[0132] In formula (B2), -(R ２５ O) ｍ４ - is preferably represented by the above formula (A4).

[0133] In formula (B2), R ２６ is R in formula (B1). ２３ Corresponds to R ２３ When R contains a hydrogen atom, ２６ is R ２３ is a group in which all hydrogen atoms in R have been substituted with fluorine atoms. ２３ When does not contain a hydrogen atom, R ２６ is R ２３ is the same as

[0134] In formula (B2), m4 corresponds to m2 in formula (B1). m4 is the same as m2.

[0135] R ＢＦ１ Specific examples of the structure include the following: * represents the bonding site with —O—(C═O)—.

[0136]

[0137] [R ＡＦ２ ] In formula (4), R ＡＦ２ is R Ａ２ is a group corresponding to Ａ２ When contains a hydrogen atom, R ＡＦ２ is R Ａ２ R is a group in which all hydrogen atoms present in R have been substituted with fluorine atoms. Ａ２ When does not contain a hydrogen atom, R ＡＦ２ is R Ａ２ is the same group as

[0138] From the viewpoint of excellent solubility in solvents, R ＡＦ２ is preferably represented by the following formula (A6): ＡＦ２ Preferably, —R further has an ether bond. ３４ O-(R ３５ O) ｍ６ -R ３６ - ... (A6)

[0139] In formula (A6), R ３４ and R ３６are 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.

[0140] In formula (A6), R ３４ and R ３６ are R in formula (A5), respectively. ３１ and R ３３ Corresponds to R ３１ When R contains a hydrogen atom, ３４ is R ３１ is a group in which all hydrogen atoms in R have been substituted with fluorine atoms. ３１ When does not contain a hydrogen atom, R ３４ is R ３１ It is the same as R ３３ When R contains a hydrogen atom, ３６ is R ３３ is a group in which all hydrogen atoms in R have been substituted with fluorine atoms. ３３ When does not contain a hydrogen atom, R ３６ is R ３４ is the same as

[0141] In formula (A6), -(R ３５ O) ｍ６ - represents -(R ３２ O) ｍ５ Corresponds to -. R ３２ When R contains a hydrogen atom, ３５ is R ３２ is a group in which all hydrogen atoms in R have been substituted with fluorine atoms. ３２ When does not contain a hydrogen atom, R ３５ is R ３２ is the same as

[0142] In formula (A6), R ３４ and R ３６ R in formula (A5) ３１ and R ３３ In formula (A6), -(R ３５ O) ｍ６ - is -(R ３２ O) ｍ５ - and the same as above.

[0143] R ＡＦ２ Specific examples of the structure include the following: * represents the bonding site with —O—, and n2 represents an integer of 0 to 200.

[0144]

[0145] [R ＢＦ２ and R ＢＦ３ ] In formula (4), R ＢＦ２ and R ＢＦ３ are respectively R Ｂ２ and R Ｂ３ is a group corresponding to Ｂ２ When contains a hydrogen atom, R ＢＦ２ is R Ｂ２ R is a group in which all hydrogen atoms present in R have been substituted with fluorine atoms. Ｂ２ When does not contain a hydrogen atom, R ＢＦ２ is R Ｂ２ is the same group as Ｂ３ When contains a hydrogen atom, R ＢＦ３ is R Ｂ３ R is a group in which all hydrogen atoms present in R have been substituted with fluorine atoms. Ｂ３ When does not contain a hydrogen atom, R ＢＦ３ is R Ｂ３ is the same group as

[0146] R ＢＦ２ or R ＢＦ３ is a group represented by R in formula (3) ＢＦ１ Examples of the groups include the same groups as those represented by the following formula:

[0147] The number average molecular weight of the fluorine-containing compound is not particularly limited, and may be, for example, 100 to 101,000. From the viewpoint of excellent solubility in solvents, it is preferably 100 to 21,000, more preferably 300 to 11,000, and even more preferably 400 to 7,000. １ H-NMR and １９ It is the number average molecular weight of each molecule calculated from the molecular structure identified by F-NMR.

[0148] The present disclosure will be described in more detail below with reference to examples, but the present disclosure is not limited to the following examples as long as it does not deviate from the gist of the disclosure. Among Examples 1 to 4, Examples 1 to 3 are working examples, and Example 4 is a comparative example.

[0149] Below, CF ３ CF ２ CF ２ OCF (CF ３ )CF ２ OCF (CF ３ )C(=O)F(HFPO) ３ It is written as follows.

[0150] <Example 1> (Internal fluorination operation) Nitrogen gas was blown into a 500 mL SUS316 autoclave for 1 hour, and then the pressure inside the autoclave was increased to 0.100 MPa with fluorine gas diluted to 20% by volume with nitrogen gas (also referred to as "20% by volume fluorine gas"), and the autoclave was maintained for 5 hours to perform an internal fluorination operation, and this was used as a reactor. Thereafter, the 20% by volume fluorine gas inside the reactor was extracted, and nitrogen gas was blown in for 2 hours.

[0151] (Preparation of raw material solution) On the other hand, the raw material compound CH ３ CH ２ OCH ２ CH ２ OCH ２ CH ２ OCOCF (CF ３ ) OCF ２ CF (CF ３ ) OCF ２ CF ２ CF ３ 10g of (HFPO) ３ This was dissolved in 240 g of CH ３ CH ２ OCH ２ CH ２ OCH ２ CH ２ OCOCF (CF ３ ) OCF ２ CF (CF ３ ) OCF ２ CF ２ CF ３was prepared according to Example 1 (Step 1-1) of WO 2008 / 026707. (HFPO) ３ The used was a product manufactured by AGC.

[0152] (Fluorination of Raw Material Compounds) The autoclave that had undergone the above-described internal fluorination operation was charged with (HFPO). ３ 200 g of fluorine gas was added and stirred, and nitrogen gas was blown in for 1 hour. Thereafter, 20% by volume fluorine gas was blown in at a flow rate of 5.66 L / hour for 1 hour, and while blowing in at the same flow rate, the raw material solution was injected over 5 hours. Next, while blowing in 20% by volume fluorine gas while maintaining the above flow rate, (HFPO) of benzene was added. ３ 20 mL of a solution (0.01 g / mL) was poured into the flask and stirred for 1 hour. Nitrogen gas was then blown into the flask for 2 hours, and the resulting crude liquid was concentrated using an evaporator. １９ F-NMR and １ The product was quantified by H-NMR. The fluorination rate determined by the above method was 88%.

[0153] Example 2 The same procedure as in Example 1 was carried out, except that a 500 mL Ni autoclave was used instead of the SUS316 autoclave. １９ The product was quantitatively analyzed by F-NMR, and the fluorination rate was found to be 89%.

[0154] Example 3 The same procedure as in Example 1 was carried out, except that a 500 mL SUS316 autoclave lined with PFA resin was used instead of the SUS316 autoclave, and the internal surface fluorination procedure was not carried out. １９ The product was quantitatively analyzed by F-NMR, and the fluorination rate was found to be 87%.

[0155] Example 4 The same procedure as in Example 1 was carried out, except that a 500 mL SUS316 autoclave was used for the test without carrying out the internal fluorination procedure. １９ The product was quantitatively analyzed by F-NMR, and the fluorination rate was found to be 75%.

[0156] <Measurement of Pressure Change> In order to confirm whether the inner surface of the reactor in each example was inert to fluorine gas, the pressure change was measured as follows. Specifically, after the test in each example was carried out, in order to check the state of the reactor, nitrogen gas was blown into each autoclave for 1 hour, and then the pressure inside the autoclave was increased with 20% by volume fluorine gas until it reached 0.100 MPa, and this was maintained for 5 hours, and the pressure change was measured. A pressure change of 0.001 MPa or less was evaluated as A, and a pressure change of more than 0.001 MPa was evaluated as B. The results are shown in Table 1.

[0157] <Evaluation of corrosion resistance> In each example, the fluorination operation of the raw material compound was repeated until the flow of 20% by volume fluorine gas exceeded 72 hours in total, and the wall thickness of the reactor was measured before and after the operation. The wall thickness loss rate (unit: mm / year) per year (i.e., 8,760 hours) was calculated from the difference between the measured values. A wall thickness loss rate of less than 0.1 mm / year was evaluated as A, and a wall thickness loss rate of 0.1 mm / year or more was evaluated as B. The results are shown in Table 1.

[0158] The material of the reactor body, the components contained in the surface layer on the inner surface of the reactor, and the fluorination rate in Examples 1 to 4 are also shown in Table 1. In the table, "-" indicates that no surface layer was provided on the inner surface of the reactor.

[0159]

[0160] As shown in Table 1, Examples 1 to 3 have higher fluorination rates than Example 4. It is believed that Examples 1 to 3 have higher corrosion resistance of the reactor than Example 4, which is why the high fluorination rates were achieved.

[0161] The method for producing a fluorine-containing compound according to the present disclosure can produce a fluorine-containing compound with a high fluorination rate. The obtained fluorine-containing compound can be derived into a fluorine-containing compound having various functional groups (e.g., a hydroxyl group, an ethylenically unsaturated group, an epoxy group, a carboxy group, etc.). Furthermore, the obtained fluorine-containing compound and fluorine-containing compounds that can be derived from the fluorine-containing compound can be used as a surface treatment agent, an emulsifier, rubber, a surfactant, a solvent, a heat transfer medium, a pharmaceutical, an agricultural chemical, a lubricating oil, an intermediate thereof, etc.

[0162] The disclosure of Japanese Patent Application No. 2022-185979, filed on November 21, 2022, is incorporated herein by reference in its entirety. All documents, patent applications, and technical standards described herein are incorporated herein by reference to the same extent as if each individual document, patent application, and technical standard was specifically and individually indicated to be incorporated by reference.

Claims

1. A method for producing a fluorine-containing compound, which comprises fluorinating an organic compound having at least one fluorinable atom in a composition containing the organic compound in a reactor having an inner surface inert to fluorine gas by introducing a gas containing fluorine gas into the composition.

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 the holding is 0.001 MPa or less.

3. The method for producing a fluorine-containing compound according to Claim 1, wherein the inner surface inert 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 having an inner surface made inert 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 inert 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 containing at least one element selected from the group consisting of nickel, copper, aluminum, chromium, iron, silver, titanium, and molybdenum, and a surface layer located on the inner surface of the reactor body and inert 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 liquid 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.