WO2024111491A1

WO2024111491A1 - Production method for fluorine-containing compound and fluorine-containing compound

Info

Publication number: WO2024111491A1
Application number: PCT/JP2023/041156
Authority: WO
Inventors: 貴史川上; 知広林; 貴行酒井; 元志青山
Original assignee: Ａｇｃ株式会社
Priority date: 2022-11-21
Filing date: 2023-11-15
Publication date: 2024-05-30

Abstract

A production method for a fluorine-containing compound wherein an organic compound having at least one atom that can be fluorinated is fluorinated in a liquid containing said organic compound to obtain a fluorine-containing compound that is a fluorinated substance in which the average number of atoms that can be fluorinated per molecule is at least 0.01.

Description

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

This disclosure relates to a method for producing a fluorine-containing compound and the fluorine-containing compound.

There are various known methods for fluorinating an organic compound having a fluorinatable atom such as a hydrogen atom. For example, a method of fluorination using fluorine gas is known.
Patent Document 1 discloses a method for fluorinating an organic compound having a fluorinatable atom by supplying fluorine gas to a liquid phase containing the organic compound and an organic solvent.

International Publication No. 2000/056694

Among fluorine-containing compounds, many of the fully fluorinated compounds in which all fluorinatable atoms are replaced with fluorine atoms have high heat resistance and are useful, for example, as heat transfer media.
When a completely fluorinated fluorine-containing compound is to be produced by fluorinating a compound having a fluorinatable atom, it is generally necessary to make the fluorination reaction conditions severe, such as by lengthening the fluorination time, increasing the reaction temperature, increasing the reaction pressure, or, in the case of fluorination with fluorine gas, increasing the amount of fluorine gas.
However, as described above, when fluorination is performed under harsh reaction conditions such as prolonging the fluorination time, side reactions such as decomposition reactions are likely to occur, and the yield of the target fluorine-containing compound is likely to be low. In addition, since a liquid containing a large amount of fully fluorinated products is likely to have a high viscosity, for example, when removing impurities by filtration after fluorination, the filtrate is likely to remain in a filtration device, etc., and the yield of the target fluorine-containing compound is likely to be further reduced.

The objective of one embodiment of the present invention is to provide a method for producing a fluorine-containing compound that can produce the target fluorine-containing compound in high yield, and to provide the fluorine-containing compound.

The present disclosure includes the following aspects.
＜1＞
A method for producing a fluorine-containing compound, comprising fluorinating an organic compound having at least one fluorinatable atom in a liquid containing the organic compound, thereby obtaining a fluorinated product having an average number of the fluorinatable atoms per molecule of 0.01 or more.
＜2＞
The method for producing a fluorine-containing compound according to <1>, wherein the average number of the fluorinatable atoms per molecule is 5 or less.
＜3＞
The method for producing a fluorine-containing compound according to <1> or <2>, wherein the organic compound has a hydrogen atom as the fluorinatable atom.
＜4＞
The method for producing a fluorine-containing compound according to any one of <1> to <3>, wherein the organic compound is fluorinated by introducing a gas containing fluorine gas into the liquid.
＜5＞
The method for producing a fluorine-containing compound according to any one of <1> to <4>, wherein the liquid is retained in a reactor in which the fluorination is carried out for 200 hours or less.
＜6＞
The method for producing a fluorine-containing compound according to any one of <1> to <5>, wherein the liquid further contains a solvent.
＜７＞
The method for producing a fluorine-containing compound according to <6>, wherein the mass of the solvent is 10 times or less the mass of the organic compound.
＜8＞
The method for producing a fluorinated compound according to any one of <1> to <7>, wherein the fluorination temperature is 5 to 50° C.
＜9＞
The method for producing a fluorine-containing compound according to any one of <1> to <8>, wherein the organic compound has a number average molecular weight of 800 to 28,000.
＜10＞
A fluorine-containing compound having an average number of hydrogen atoms per molecule of 0.01 to 5 and a number average molecular weight of 1,000 to 30,000.
<11>
The fluorine-containing compound according to <10>, which contains a fluoropolyether chain.

The present disclosure provides a method for producing a fluorine-containing compound and a fluorine-containing compound that can produce the desired fluorine-containing compound in high yield.

Below, the form for carrying out the 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, the components (including element steps, etc.) are not essential unless specifically stated otherwise. The same applies to numerical values and their ranges, and they do not limit the embodiments of the present disclosure.

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 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 the present disclosure. In addition, 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, combinations of two or more preferred aspects are more preferred aspects.
In the present disclosure, when there are multiple substances corresponding to each component, the amount of each component means 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).

[Method of producing fluorine-containing compound]
In a method for producing a fluorinated compound according to an embodiment of the present disclosure, an organic compound having at least one fluorinable atom is fluorinated in a liquid containing the organic compound, thereby obtaining a fluorinated compound having an average number of the fluorinable atoms per molecule of 0.01 or more.
Hereinafter, an organic compound having at least one fluorinable atom is also referred to as a "raw material compound," and the average number of the fluorinable atoms per molecule is also referred to as the "remaining number of atoms."

In the above-mentioned method for producing a fluorine-containing compound, the target fluorine-containing compound can be obtained in high yield.
Specifically, by making the target substance into a fluorinated substance having 0.01 or more residual atoms, the target substance can be easily obtained even under mild reaction conditions for fluorination, and therefore by making the reaction conditions mild, side reactions are suppressed and the yield of the target fluorine-containing compound is increased. In addition, by making the target substance into a fluorinated substance having 0.01 or more residual atoms, the viscosity of the liquid after fluorination can be kept low, so that even when removing impurities by filtration, for example, the filtrate is less likely to remain in a filtration device or the like, and the yield of the target fluorine-containing compound is increased.

<Number of remaining atoms>
The number of remaining atoms is the average number of "fluorinable atoms" that the fluorine-containing compound of interest has in one molecule.For example, when the fluorine-containing compound obtained by fluorinating the raw material compound is a mixture in which 3 molecules have one fluorinable atom remaining and 7 molecules have all fluorinable atoms replaced with fluorine atoms in 10 molecules, the number of remaining atoms of the fluorine-containing compound is 0.3.In this case, the 3 molecules with one fluorinable atom remaining may be fluorinable atoms remaining at different positions among the fluorinable atoms of the raw material compound, or may be fluorinable atoms remaining at the same position.

Furthermore, the fluorine-containing compound having a remaining atom number of 0.3 is not limited to the above-mentioned form, and may be a mixture in which, for example, among 10 molecules, there is one molecule having two remaining fluorinable atoms, one molecule having one remaining fluorinable atom, and seven molecules in which all fluorinable atoms have been replaced with fluorine atoms.
In other words, a fluorine-containing compound having a remaining number of atoms of 0.01 or more may be a mixture of molecules having different numbers of remaining fluorinable atoms. In particular, a fluorine-containing compound having a remaining number of atoms of 0.01 or more and less than 1 is a mixture of molecules having one or more remaining fluorinable atoms and molecules in which all fluorinable atoms have been replaced with fluorine atoms.
When the fluorine-containing compound has two or more types of fluorinable atoms, the number of remaining atoms is the total average number of the two or more types of fluorinable atoms.

The number of remaining atoms is calculated as follows.
Specifically, for example, when the fluorinable atom is a hydrogen atom, the number of remaining atoms can be determined from the hydrogen atom peak area obtained from ¹ H-NMR, and the number of remaining atoms can be determined from the ratio of the peak area of fluorine atoms bonded to a carbon atom to which a fluorinable atom is bonded, obtained from ¹⁹ F-NMR, to the peak area of fluorine atoms bonded to a carbon atom to which no fluorinable atom is bonded, obtained from ¹⁹ F-NMR.

The number of remaining atoms is preferably 0.01 or more and 5 or less. A fluorine-containing compound having 5 or less remaining atoms has high heat resistance and is useful, for example, as a heat transfer medium, even if it is not a fully fluorinated compound, that is, a fluorine-containing compound having 0 remaining atoms.
In other words, by fluorinating a raw material compound in a liquid containing the raw material compound to obtain a fluorinated compound having a residual atom number of 0.01 to 5, a fluorinated compound having high heat resistance can be obtained in high yield.
From the viewpoint of achieving both a high yield and high heat resistance, the number of residual atoms is more preferably 0.01 to 4, further preferably 0.01 to 1, and particularly preferably 0.01 to 0.5.

Examples of the atom that can be fluorinated include a hydrogen atom, a bromine atom, an iodine atom, and a chlorine atom, with a hydrogen atom being preferred.
The average number of "hydrogen atoms" that the target fluorine-containing compound has in one molecule is preferably 0.01 or more, more preferably 0.01 to 5, even more preferably 0.01 to 4, particularly preferably 0.01 to 1, and extremely preferably 0.01 to 0.5. Hereinafter, the average number of hydrogen atoms that the target fluorine-containing compound has in one molecule is also referred to as the "residual H number."

The number of remaining atoms and the number of remaining H can be controlled, for example, by adjusting the reaction conditions in the fluorination of the raw material compound. Specific examples of the reaction conditions include the fluorination time, reaction temperature, reaction pressure, etc. In addition, when the raw material compound is fluorinated with fluorine gas, the amount and concentration of fluorine gas introduced into the liquid can also be included as reaction conditions.
Furthermore, since fluorinable atoms in the raw material compound remain unfluorinated to become fluorinable atoms in the target product, the number of remaining atoms and the number of remaining H atoms may be controlled by adjusting the number of fluorinable atoms and hydrogen atoms per molecule in the raw material compound.

<Fluorination reaction>
Examples of methods for fluorinating a raw material compound in a liquid include the ECF method, the cobalt fluorination method, and a method of reacting with fluorine. Among these, the method of reacting with fluorine, which can advantageously advance the fluorination of the raw material compound, is preferred.

In the method of reacting a raw material compound with fluorine in a liquid, for example, a gas containing fluorine gas is introduced into a liquid containing the raw material compound.
As an example of the fluorination reaction, a method of introducing a gas containing fluorine gas into a liquid containing a raw material compound will be described below, but the present invention is not limited to this.

The gas introduced into the liquid should 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 such as nitrogen gas, helium gas, neon gas, and argon gas, with nitrogen gas or helium gas being preferred, and nitrogen gas being preferred from the viewpoint of keeping costs low.

The content of fluorine gas in the entire gas is preferably 10% by volume or more, more preferably 15% by volume or more, even more preferably 20% by volume or more, and particularly preferably 25% by volume or more, from the viewpoint of easily controlling the number of remaining atoms of the target substance. Furthermore, 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 viewpoint of easily controlling the number of remaining atoms of the target substance. From the above viewpoint, the content of fluorine gas in the entire gas is preferably 10 to 60% by volume, more preferably 15 to 50% by volume, even more preferably 20 to 40% by volume, and particularly preferably 25 to 40% by volume.

The temperature for fluorinating the raw material compound is, for example, in the range of −60° C. or more and the boiling point of the raw material compound or less, and may be in the range of −50 to 100° C. or may be in the range of −20 to 50° C. The temperature for fluorinating the raw material compound is preferably 5 to 50° C., more preferably 5 to 40° C., and even more preferably 10 to 30° C., from the viewpoint of setting the number of remaining atoms of the target product in the above range.
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 in a batch manner or in a continuous manner.

The time for which a liquid containing the raw material compound and into which fluorine gas has been introduced remains in a reactor in which the raw material compound is fluorinated is, from the viewpoint of keeping the number of remaining atoms of the target product within the above-mentioned range, preferably 200 hours or less, more preferably 190 hours or less, and even more preferably 170 hours or less. Hereinafter, the time for which the liquid remains in the reactor is also referred to as the "residence time".
From the viewpoint of keeping the number of remaining atoms of the target product within the above range, the residence time is preferably 0.3 hours or more, more preferably 0.6 hours or more, even more preferably 1.0 hour or more, particularly preferably 50 hours or more, extremely preferably 70 hours or more, and most preferably 100 hours or more. The residence time is preferably 0.3 to 200 hours, more preferably 0.6 to 200 hours, even more preferably 1.0 to 200 hours, particularly preferably 50 to 200 hours, extremely preferably 70 to 200 hours, and most preferably 100 to 200 hours.
The residence time is calculated from the flow rate of the liquid and the volume of the reactor when the fluorination of the raw material compound is carried out in a continuous manner. The residence time may be adjusted by the flow rate of the liquid and the length of the reactor in the flow direction when the fluorination of the raw material compound is carried out in a continuous manner.

<Liquid>
The liquid 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, and the like, as necessary.

(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.
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 200, preferably 5 to 100, and more preferably 10 to 50. In other words, the average number of "fluorinable atoms" contained in one molecule of the raw material compound is, for example, 1 to 200, preferably 5 to 100, and more preferably 10 to 50.

Examples of the fluorinable atom include a hydrogen atom, a bromine atom, an iodine atom, a chlorine atom, etc., and among these, a hydrogen atom is preferable. The raw material compound preferably has a hydrogen atom as a fluorinable atom.
The number of hydrogen atoms contained in one molecule of the raw material compound is, for example, 1 to 200, preferably 5 to 100, and more preferably 10 to 50. In other words, the average number of hydrogen atoms contained in one molecule of the raw material compound is, for example, 1 to 200, preferably 5 to 100, and more preferably 10 to 50.

The number average molecular weight of the raw material compound is, for example, 800 to 100,000. From the viewpoint of easily controlling the number of residual atoms and of suppressing side reactions to obtain a high yield, it is preferably 800 to 28,000, more preferably 800 to 20,000, even more preferably 800 to 10,000, particularly preferably 1,000 to 10,000, extremely preferably 1,000 to 8,000, and most preferably 2,000 to 6,000.
The number average molecular weight of the raw material compound is a value calculated from the molecular structure identified by ¹ H-NMR and ¹⁹ F-NMR.

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, 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."

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, a sulfonyl group, etc. Examples of the specific functional group include a carbonyl group other than an ester bond and an amide bond.
The raw material compound is preferably a compound having, as a specific functional group, 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, 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.

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 carbonyl group of the ester bond. The raw material compound may also 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 carbonyl group of the ester bond.

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

In formulas (1) and (2),
R ^A1 , R ^B1 , R ^B2 , and R ^B3 each independently represent 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.

In the present disclosure, a "monovalent saturated hydrocarbon group" may be any of a linear alkyl group, a branched alkyl group, and a cycloalkyl group. A "divalent saturated hydrocarbon group" may 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.

In this disclosure, "halogeno" means that one or more hydrogen atoms present in the group are replaced 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.

In this disclosure, a "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 replaced by a halogen atom. A "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 replaced by a halogen atom.

In this disclosure, "heteroatom" means an atom other than a carbon atom or a hydrogen atom, and examples include a nitrogen atom, an oxygen atom, and a sulfur atom.

In the present disclosure, a "heteroatom-containing monovalent saturated hydrocarbon group" refers to a group in which a divalent heteroatom or a divalent group containing a heteroatom is contained in a monovalent saturated hydrocarbon group. A "heteroatom-containing divalent saturated hydrocarbon group" refers to a group in which a divalent heteroatom or a divalent group containing a heteroatom is contained in a divalent saturated hydrocarbon group. Examples of divalent heteroatoms include -O- and -S-. Examples of divalent groups containing a heteroatom include -NH-, -C(=O)-, and _-SO2- .

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 heteroatom-containing monovalent saturated hydrocarbon group have been replaced with a halogen atom. The term "halogeno (heteroatom-containing divalent saturated hydrocarbon) group" refers to a group in which one or more hydrogen atoms in the heteroatom-containing divalent saturated hydrocarbon group have been replaced with a halogen atom.

In formula (1), it is preferable that at least one of R ^A1 and R ^B1 contains a hydrogen atom. Also, in formula (2), it is preferable that at least one selected from the group consisting of R ^A2 , R ^B2 , and R ^B3 contains a hydrogen atom.

[R ^A1 ]
In formula (1), R ^A1 represents 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.

Examples of the monovalent saturated hydrocarbon group represented by R ^A1 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.

The halogeno monovalent saturated hydrocarbon group represented by R ^A1 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.

The heteroatom-containing monovalent saturated hydrocarbon group represented by R ^A1 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.

The halogeno (heteroatom-containing monovalent saturated hydrocarbon) group represented by R ^A1 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.

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

In particular, from the viewpoint of excellent solubility in liquids, R ^A1 is preferably represented by the following formula (A1): In other words, R ^A1 preferably further has an ether bond, and more preferably includes at least one selected from the group consisting of a polyether chain and a fluoropolyether chain.
R ¹¹ O-(R ¹² O) _m1 -R ¹³ - ... (A1)

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

In formula (A1), examples of R ¹¹ include an alkyl group and a fluoroalkyl group.

The carbon number of R ¹¹ 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.

The alkyl group represented by R ¹¹ may be a linear alkyl group, a branched alkyl group, or an alkyl group having a ring structure.

The fluoroalkyl group represented by R ¹¹ may be a straight-chain fluoroalkyl group, a branched-chain fluoroalkyl group, or a fluoroalkyl group having a ring structure.

Among these, 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.

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 a fluoroalkylene group having 1 carbon atom;
R ^f2 is a fluoroalkylene group having 2 carbon atoms,
R ^f3 is a fluoroalkylene group having 3 carbon atoms,
R ^f4 is a fluoroalkylene group having 4 carbon atoms,
R ^f5 is a fluoroalkylene group having 5 carbon atoms;
R ^f6 is a fluoroalkylene group having 6 carbon atoms.
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.

From the viewpoint of excellent solubility in liquids, k1+k2+k3+k4+k5+k6 is preferably an integer from 1 to 500, more preferably an integer from 1 to 300, even more preferably an integer from 5 to 200, and particularly preferably an integer from 10 to 150.

In addition, 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 arrangement. For example, (R ^f5 O) _k5 represents that the number of (R ^f5 O) is k5, and does not represent a block arrangement structure of (R ^f5 O) _k5 . Similarly, the order of (R ^f1 O) to (R ^f6 O) does not represent the bonding order of each unit.

In R ^f3 to R ^f6 , the fluoroalkylene group may be a linear fluoroalkylene group, a branched fluoroalkylene group, or a fluoroalkylene group having a ring structure.

Specific examples of R ^f1 include --CF ₂ -- and --CHF--.

Specific examples of R ^f2 include -CF ₂ CF ₂ -, -CF ₂ CHF-, -CHFCF ₂ -, -CHFCHF-, -CH ₂ CF ₂ -, and -CH ₂ CHF-.

Specific examples of R ^f3 include -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 2 CH 2} _CHF- _, _-CF (CF ₃ )-CF ₂ -, -CF(CHF ₂ )-CF ₂ -, -CF(CH ₂ F)-CF ₂ -, -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( _CH2 Examples of such groups include -CH(CH ₃ )-CHF-, -CH(CH 3 )-CHF-, -CH(CF ₃ )-CH ₂ -, -CH(CHF ₂ )-CH ₂ -, and -CH(CH ₂ F)-CH ₂ -.

Specific examples of R ^f4 include -CF ₂ CF ₂ CF ₂ _- , -CF ₂ 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} _CHFCFCF ₂ _- _, _and _-CF ₂ _CHFCFCF 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 CH ₂ _{CH 2} _CHF- , and -cycloC ₄ F ₆ -.

Specific examples of R ^f5 include -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 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 Examples include -CF ₂ -, -CH ₂ CF ₂ CHFCF ₂ CF ₂ -, -CH ₂ CF ₂ CF ₂ CF ₂ CH ₂ -, and -cycloC ₅ F ₈ -.

Specific examples of R ^f6 include -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 _{CH 2} _- , and -cycloC ₆ F ₁₀ -.
Here, -cycloC ₄ F ₆ - means a perfluorocyclobutanediyl group, a specific example of which is a perfluorocyclobutane-1,2-diyl group, -cycloC ₅ F ₈ - means a perfluorocyclopentanediyl group, a specific example of which is a perfluorocyclopentane-1,3-diyl group, -cycloC ₆ F ₁₀ - means a perfluorocyclohexanediyl group, a specific example of which is a perfluorocyclohexane-1,4-diyl group.

Among these, —(R ¹² O) _m1 — preferably contains at least one selected from the group consisting of structures represented by the following formulas (F1) to (F3), and more preferably contains 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)
However, the symbols in formulas (F1) to (F3) are the same as those in formula (A2) above.

In formula (F1) and formula (F2), the bonding order of (R ^f1 O) and (R ^f2 O), and (R ^f2 O) and (R ^f4 O) are each arbitrary. For example, (R ^f1 O) and (R ^f2 O) may be arranged alternately, (R ^f1 O) and (R ^f2 O) may be arranged in blocks, or may be arranged randomly. The same applies to formula (F2).
In formula (F1), k1 is preferably an integer of 1 to 30, and more preferably an integer of 1 to 20. Also, k2 is preferably an integer of 1 to 30, and more preferably an integer of 1 to 20.
In formula (F2), k2 is preferably an integer of 1 to 30, and more preferably an integer of 1 to 20. Also, k4 is preferably an integer of 1 to 30, and more preferably an integer of 1 to 20.
In formula (F3), k3 is preferably an integer of 1 to 30, and more preferably an integer of 1 to 20.

In formula (A1), examples of R ¹³ include the same as R ^f1 to R ^f6 above.

Of these, R ¹³ is preferably a fluoroalkylene group having 1 to 4 carbon atoms.

Specific examples of R ^A1 include the following structures. * represents a bonding site with --O--, n1 represents an integer of 0 to 60, and n2 represents an integer of 0 to 500. n1 is, for example, 13, and n2 is, for example, 7.

[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.

Examples of the monovalent saturated hydrocarbon group represented by R ^B1 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.

The halogeno monovalent saturated hydrocarbon group represented by R ^B1 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.

The heteroatom-containing monovalent saturated hydrocarbon group represented by ^R 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. In other words, R ^preferably further has an ether bond.

The halogeno (heteroatom-containing monovalent saturated hydrocarbon) group represented by R ^B1 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.

The carbon number of R ^B1 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.

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

Among these, from the viewpoint of excellent solubility in a solvent described later, R ^B1 is preferably represented by the following formula (B1).
^R21O- ( ^R22O ) _m2 - ^R23 -... (B1)

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

In formula (B1), examples of R ²¹ include an alkyl group and a fluoroalkyl group.

The carbon number of R ²¹ 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.

The alkyl group represented by ^R21 may be a linear alkyl group, a branched alkyl group, or an alkyl group having a ring structure.
The fluoroalkyl group represented by R ²¹ may be a straight-chain fluoroalkyl group, a branched-chain fluoroalkyl group, or a fluoroalkyl group having a ring structure.

Among these, 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.

In formula (B1), —(R ²² O) _m2 — is preferably represented by the above formula (A2).

In formula (B1), m2 is preferably 0 to 15, more preferably 0 to 10, even more preferably 0 to 4, and particularly preferably 0 to 2.

In formula (B1), examples of R ²³ include the same as R ^f1 to R ^f6 above.

Among these, 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.

Specific examples of R ^B1 include the following structures: * represents the bonding site with -O-(C=O)-.

[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.

Examples of 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 ^R include groups in which one hydrogen atom or one halogen atom has been removed from 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 R in ^{formula (} 1).

The carbon number of R ^A2 is preferably 1 to 200, and more preferably 3 to 100, from the viewpoint of excellent solubility in a solvent described later.

Among these, from the viewpoint of excellent solubility in a solvent described later, R ^A2 is preferably represented by the following formula (A5): In other words, R ^A2 preferably further has an ether bond, and more preferably includes at least one selected from the group consisting of a polyether chain and a fluoropolyether chain.
-R ³¹ O-(R ³² O) _m5 -R ³³ - ... (A5)

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

In formula (A5), R ³¹ and R ³³ each independently have the same meaning as R ¹³ in formula (A1).
In formula (A5), examples of -(R ³² O) _m5 - include the same as -(R ¹² O) _m1 - in formula (A1).

Specific examples of R ^A2 include the following structures: * represents a bonding site with —O—, and n2 represents an integer of 0 to 500.

[R ^B2 and R ^B3 ]
In formula (2), R ^B2 and R ^B3 each independently represent 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.

Examples of 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 R ^or ^R include groups similar to 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 R in ^formula (1).

An example of a raw material compound is the following compound (T1).

From the viewpoint of viscosity, the content of the raw material compound contained in the liquid is preferably 10 to 100% by mass, more preferably 10 to 70% by mass, even more preferably 15 to 70% by mass, and particularly preferably 20 to 50% by mass, based on the total mass of the liquid.

(solvent)
The liquid may contain a solvent as necessary. The solvent is not particularly limited as long as it can dissolve the raw material compound.

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 that contains chlorine atoms. The chlorine-containing solvent preferably contains fluorine atoms in addition to chlorine atoms.

Examples of chlorine-containing solvents include CClF ₂ CClFCF ₂ OCF ₂ CClF ₂ (CFE-419), CH ₂ ClCHClCH ₂ OCF ₂ CHFCl (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 HCClFCF ₂ OCF ₂ CF ₂ Cl (HCFE-429), and the like.
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.

The boiling point of the solvent is preferably from 10 to 500°C, more preferably from 30 to 250°C, and even more preferably from 50 to 150°C, from the viewpoint of improving the yield of the fluorine-containing compound.
The solvent preferably has 4 or more carbon atoms, 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.
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 the molecular weight has a distribution, the molecular weight represents the mass average molecular weight (Mw). Mw is measured in terms of polystyrene by gel permeation chromatography (GPC) measurement using tetrahydrofuran (THF) as an eluent.

The liquid contains a solvent, and the mass of the solvent is preferably 10 times or less, more preferably 5 times or less, and even more preferably 3 times or less, the mass of the raw material compound. By having the mass of the solvent in the above range relative to the mass of the raw material compound, there is an advantage that the amount of solvent used and the amount of raw material solution can be reduced, thereby making it possible to make the reaction apparatus smaller. Furthermore, when the number of remaining atoms of the target fluorine-containing compound is 0.01 or more, the viscosity of the liquid after fluorination can be kept low, so the amount of solvent can be reduced, and even when impurities are removed by filtration, filtrate is less likely to remain in the filtration device, etc., and the yield of the target fluorine-containing compound is increased.

(Other additives)
The liquid may contain other additives as necessary, such as an auxiliary agent that promotes the fluorination of the raw material compound.
Examples of the auxiliary include a C-H bond-containing compound and a carbon-carbon double bond-containing compound other than the raw material compound. Examples of the C-H bond-containing compound include benzene and toluene. Examples of the carbon-carbon double bond-containing compound include hexafluoropropylene and hexafluorobutadiene. Among these, the auxiliary is preferably an aromatic hydrocarbon such as benzene or toluene.
In this embodiment, since the number of remaining atoms of the target fluorine-containing compound is 0.01 or more, the target fluorine-containing compound can be obtained in high yield by direct fluorination with fluorine gas in the liquid even if the liquid does not contain an auxiliary. Therefore, the liquid does not need to contain the above-mentioned auxiliary.

<Fluorine-containing compounds>
The fluorine-containing compound obtained by fluorinating a raw material compound is a compound in which at least one fluorinatable atom of the raw material compound is replaced with a fluorine atom and the number of remaining atoms is 0.01 or more.
As described above, a fluorine-containing compound having 0.01 or more residual atoms may be a mixture of molecules having different numbers of fluorinable atoms. In particular, a fluorine-containing compound having 0.01 or more and less than 1 residual atom is a mixture of molecules having one or more fluorinable atoms and molecules having no fluorinable atoms.
In addition, when there are a plurality of molecules having one or more fluorinable atoms, the plurality of molecules may have the fluorinable atoms at different positions or at the same position.

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

The fluorine-containing compound is preferably a compound in which the average number of hydrogen atoms among fluorinable atoms per molecule is 0.01 to 5 and the number average molecular weight is 1,000 to 30,000.
The average number of hydrogen atoms per molecule in the fluorine-containing compound is more preferably from 0.01 to 4, further preferably from 0.01 to 1, and particularly preferably from 0.01 to 0.5.
The number average molecular weight of the fluorine-containing compound is, for example, 800 to 101,000, and from the viewpoint of excellent solubility in a solvent, it is preferably 800 to 29,000, more preferably 800 to 21,000, even more preferably 800 to 11,000, particularly preferably 1,000 to 11,000, extremely preferably 1,000 to 9,000, and most preferably 2,000 to 7,000. The number average molecular weight of the fluorine-containing compound is the number average value of the molecular weight of each molecule calculated from the molecular structure specified by ¹ H-NMR and ¹⁹ F-NMR.

The fluorine-containing compound is preferably a compound having a specific functional group which is a divalent or higher functional group containing at least one of an oxygen atom and a sulfur atom.
The details and preferred form of the specific functional group are the same as those of the specific functional group in the above-mentioned starting compound.

When the raw material compound is a compound represented by formula (1), the fluorine-containing compound is preferably a mixture of molecules having different numbers of hydrogen atoms among compounds represented by formula (6) below. When the raw material compound is a compound represented by formula (2), the fluorine-containing compound is preferably a mixture of molecules having different numbers of hydrogen atoms among compounds represented by formula (7) below.
R ^AF1 -O-(C=O)-R ^BF1 ... (6)
R ^BF2 -(C=O)-OR ^AF2 -O-(C=O)-R ^BF3 ... (7)
In formulas (6) and (7),
R ^AF1 , R ^BF1 , R ^AF2 , R ^BF2 , and R ^BF3 are groups corresponding to R ^A1 , R ^B1 , R ^A2 , R ^B2 , and R ^B3 , respectively;
when R ^A1 , R ^B1 , R ^A2 , R ^B2 and R ^B3 are each independently a group not containing a hydrogen atom, R ^AF1 , R ^BF1 , R ^AF2 , R ^BF2 and R ^BF3 are the same group as R ^A1 , R ^B1 , R ^A2 , R ^B2 and R ^B3 ;
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 are groups in which at least a portion of the hydrogen atoms present in R ^A1 , R ^B1 , R ^A2 , R ^B2 , and R ^B3 are replaced with fluorine atoms.

The fluorine-containing compound may be a mixture of a molecule having no hydrogen atoms and a molecule having one or more hydrogen atoms, among the compounds represented by formula (6) or the compounds represented by formula (7).
That is, the compound represented by formula (6) may be a mixture of a molecule in which all hydrogen atoms in at least one of R ^A1 and R ^B1 are replaced with fluorine atoms and a molecule in which only a portion of hydrogen atoms in at least one of R ^A1 and R ^B1 are replaced with fluorine atoms. Also, the compound represented by formula (7) may be a mixture of a molecule in which all hydrogen atoms in at least one of R ^A2 , R ^B2 , and R ^B3 are replaced with fluorine atoms and a molecule in which only a portion of hydrogen atoms in at least one of R ^A2 , R ^B2 , and R ^B3 are replaced with fluorine atoms.

[R ^AF1 ]
In formula (6), R ^AF1 is a group corresponding to R ^A1 .
When ^R contains a hydrogen atom, R is ^the same ^group as R ^or a group in which at least a part of the hydrogen atoms in ^R is substituted with a fluorine atom. When R does not contain a hydrogen atom, ^R is the same group as ^R.
From the viewpoint of excellent solubility in a solvent, R ^AF1 is preferably represented by the following formula (A3).
^R14O- ( ^R15O ) _m3 - ^R16- ... (A3)

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

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

In formula (A3), -(R ¹⁵ O) _m3 - corresponds to -(R ¹² O) _m1 - in formula (A1). When R ¹² contains a hydrogen atom, R ¹⁵ is the same group as R ¹² or a group in which at least a part of the hydrogen atoms contained in R ¹² are substituted with fluorine atoms. When R ¹² does not contain a hydrogen atom, R ¹⁵ is the same as R ¹² .

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 fluoroalkylene group having 1 carbon atom;
R ^ff2 is a fluoroalkylene group having 2 carbon atoms,
R ^ff3 is a fluoroalkylene group having 3 carbon atoms,
R ^ff4 is a fluoroalkylene group having 4 carbon atoms,
R ^ff5 is a fluoroalkylene group having 5 carbon atoms,
R ^ff6 is a fluoroalkylene 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.

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

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

Among these, —(R ¹⁵ O) _m3 — preferably contains at least one selected from the group consisting of structures represented by the following formulae (G1) to (G3), and more preferably contains 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)
However, the symbols in formulas (G1) to (G3) are the same as those in formula (A4) above.

In formula (G1) and formula (G2), the bonding order of ( ^Rff1O ) and ( ^Rff2O ), and ( ^Rff2O ) and ( ^Rff4O ) are each arbitrary. For example, ( ^Rff1O ) and ( ^Rff2O ) may be arranged alternately, ( ^Rff1O ) and ( ^Rff2O ) may be arranged in blocks, or may be arranged randomly. The same applies to formula (G2).
In formula (G1), k7 is preferably an integer of 1 to 30, and more preferably an integer of 1 to 20. Furthermore, k8 is preferably an integer of 1 to 30, and more preferably an integer of 1 to 20.
In formula (G2), k8 is preferably an integer of 1 to 30, and more preferably an integer of 1 to 20. Furthermore, k10 is preferably an integer of 1 to 30, and more preferably an integer of 1 to 20.
In formula (G3), k9 is preferably an integer of 1 to 30, and more preferably an integer of 1 to 20.

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

Examples of R ¹⁶ include the same as R ^ff1 to R ^ff6 above.

Among these, R ¹⁶ is preferably a fluoroalkylene group having 1 to 3 carbon atoms.

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

Specific examples of R ^AF1 include the following structures and structures in which some of the fluorine atoms in the following structures have been replaced with hydrogen atoms. * represents a bonding site with -O-, n1 represents an integer of 0 to 60, and n2 represents an integer of 0 to 500. n1 is, for example, 13, and n2 is, for example, 7.

[R ^BF1 ]
In formula (6), R ^BF1 is a group corresponding to R ^B1 .
When ^R contains a hydrogen atom, R is ^the ^same group as R ^or a group in which at least a part of the hydrogen atoms in ^R is substituted with a fluorine atom. When ^R does not contain a hydrogen atom, R is the same group as ^R.
From the viewpoint of excellent solubility in a solvent, R ^BF1 is preferably represented by the following formula (B2).
R ²⁴ O-(R ²⁵ O) _m4 -R ²⁶ - ... (B2)

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

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

In formula (B2), -(R ²⁵ O) _m4 - corresponds to -(R ²² O) _m2 - in formula (B1). When R ²² contains a hydrogen atom, R ²⁵ is the same group as R ²² or a group in which at least a part of the hydrogen atoms contained in R ²² are substituted with fluorine atoms. When R ²² does not contain a hydrogen atom, R ²⁵ is the same as R ²² .

In formula (B2), —(R ²⁵ O) _m4 — is preferably represented by the above formula (A4).

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

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

Specific examples of R ^BF1 include the following structures and structures in which some of the fluorine atoms in the following structures have been replaced with hydrogen atoms, where * represents a bonding site with -O-(C=O)-.

[R ^AF2 ]
In formula (7), R ^AF2 is a group corresponding to R ^A2 .
When ^R contains a hydrogen atom, R is ^the same group as R ^or ^a group in which at least a part of the hydrogen atoms in ^R is substituted with a fluorine atom. When R does not contain a hydrogen atom, ^R is the same group as ^R.

From the viewpoint of excellent solubility in a solvent, R ^AF2 is preferably represented by the following formula (A6): That is, R ^AF2 preferably further has an ether bond.
^-R34O- ( ^R35O ) _m6 - ^R36- ... (A6)

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

In formula (A6), R ³⁴ and R ³⁶ correspond to R ³¹ and R ³³ in formula (A5), respectively. When R ³¹ contains a hydrogen atom, R ³⁴ is the same group as R ³¹ or a group in which at least a part of the hydrogen atoms contained in R ³¹ are substituted with fluorine atoms. When R ³¹ does not contain a hydrogen atom, R ³⁴ is the same as R ^31. When R ³³ contains a hydrogen atom, R ³⁶ is the same group as R ³³ or a group in which at least a part of the hydrogen atoms contained in R ³³ are substituted with fluorine atoms. When R ³³ does not contain a hydrogen atom, R ³⁶ is the same as R ³⁴ .

In formula (A6), -(R ³⁵ O) _m6 - corresponds to -(R ³² O) _m5 - in formula (A5). When R ³² contains a hydrogen atom, R ³⁵ is the same group as R ³² or a group in which at least a part of the hydrogen atoms contained in R ³² are substituted with fluorine atoms. When R ³² does not contain a hydrogen atom, R ³⁵ is the same as R ³² .

In formula (A6), R ³⁴ and R ³⁶ each independently have the same meaning as R ³¹ and R ³³ in formula (A5).
In formula (A6), examples of -(R ³⁵ O) _m6 - include the same as -(R ³² O) _m5 - in formula (A5).

Specific examples of R ^AF2 include the following structures and structures in which some of the fluorine atoms in the following structures have been replaced with hydrogen atoms: * represents a bonding site with —O—, and n2 represents an integer of 0 to 500.

[ ^RBF2 and ^RBF3 ]
In formula (7), R ^{3 BF2} and R ^{3 BF3} are groups corresponding to R ^{3 B2} and R ^{3 B3} , respectively.
When R ^B2 contains a hydrogen atom, R ^BF2 is the same group as R ^B2 or a group in which at least a part of the hydrogen atoms present in R ^B2 is substituted with a fluorine atom. When R ^B2 does not contain a hydrogen atom, R ^BF2 is the same group as R ^B2 .
When ^R contains a hydrogen atom, R is ^the same group as R ^or a group in which at least a part of the hydrogen atoms present in ^R is substituted with a fluorine atom. When ^R does not contain a hydrogen atom, R is ^the same group as ^R.

Examples of the group represented by R ^{3 BF2} or R ^{3 BF3} include the same groups as the group represented by R ^{3 BF1} in formula (6).

Below, the present disclosure will be explained in more detail using examples, but the present disclosure is not limited to the following examples as long as it does not exceed the gist of the disclosure. Examples 1-1 to 1-7, 2-1 to 2-4, and 3-1 to 3-3 are examples, and Examples 1-8 to 1-9 and 2-5 are comparative examples.

Hereinafter, CClF ₂ CClFCF ₂ OCF ₂ CClF ₂ will be referred to as "CFE-419".

[Examples 1-1 to 1-9]
First, CFE-419 was charged as an initial solvent into a stainless steel reactor in the amount of circulation liquid shown in the table below, and circulated through the circulation line at 300 L/hour.
Next, a raw material solution prepared by diluting a raw material compound represented by the following formula (1-1) with a solvent CFE-419 was fed to the circulation line at a flow rate under conditions such that the flow rate of the raw material compound was the raw material flow rate shown in the table below, and the flow rate of the raw material solution was the raw material solution flow rate shown in the table below.
Next, fluorine gas diluted to 30% by volume with nitrogen gas was fed into the circulation line at the gas flow rates shown in the table below.
The temperature of the circulating liquid in the circulation line was adjusted to 20° C. by a condenser.
The circulating fluid was continuously withdrawn so as to maintain the amount of the circulating fluid as shown in the table below.
The gas phase of the reactor was cooled to -10°C by a condenser, the condensate was returned to the reactor, and the gas was sent to the detoxification tower.

In the manner described above, the raw material compound was fluorinated to obtain a fluorinated product of the raw material compound, that is, a fluorine-containing compound.
The residence time during fluorination is shown in Table 1. The mass of the solvent CFE-419 was 2.33 times the mass of the raw material compound, and the pressure during fluorination was normal pressure.
The number average molecular weight of the raw material compound was 4,236, and the number average molecular weights of the fluorinated products obtained in Examples 1-1 to 1-9 were 4,956 to 5,046.
The hydrogen residues and yields of the obtained fluorinated products are shown in Table 1.

The obtained fluorinated product was subjected to a heat resistance test as follows.
A thermogravimetric/differential thermal analyzer (TG/DTA, Shimadzu Corporation, DTG-60) was used as a heat resistance tester, and the starting temperature was set at 25° C., and the temperature was raised to 500° C. at a rate of 10° C./min. The heat resistance was evaluated according to the following criteria. The results are shown in Table 1.
S: The temperature at which the weight loss is 50% is 230°C or higher. A: The temperature at which the weight loss is 50% is 220°C or higher and lower than 230°C. B: The temperature at which the weight loss is 50% is 215°C or higher and lower than 220°C. C: The temperature at which the weight loss is 50% is 210°C or higher and lower than 215°C. D: The temperature at which the weight loss is 200°C or higher and lower than 210°C. E: The temperature at which the weight loss is 50% is lower than 200°C.

[Examples 2-1 to 2-5]
The raw material compounds were fluorinated in the same manner as in Examples 1-1 to 1-9, except that the raw material solution flow rate was 0.100 kg/hour, the raw material flow rate was 0.030 kg/hour, the gas flow rate was 1200 NL/hour, the circulating liquid volume was 3.0 L, the residence time was 166 hours, and the circulating liquid temperature was adjusted to the temperatures shown in the following table, to obtain fluorinated compounds that were fluorinated products of the raw material compounds.
The mass of the solvent CFE-419 was 2.33 times the mass of the raw material compound, and the pressure during fluorination was normal pressure.
The number average molecular weight of the raw material compound was 4,236, and the number average molecular weights of the fluorinated products obtained in Examples 2-1 to 2-5 were 4,956 to 5,046.
The hydrogen residues and yields of the obtained fluorinated products are shown in Table 2.
The obtained fluorinated products were subjected to a heat resistance test in the same manner as in Examples 1-1 to 1-9 to evaluate their heat resistance. The results are also shown in Table 2.

[Examples 3-1 to 3-3]
The raw material compounds were fluorinated in the same manner as in Examples 1-1 to 1-9, except that the raw material solution flow rate was 0.100 kg/hour, the raw material flow rate was 0.030 kg/hour, the gas flow rate was 1200 NL/hour, the circulating liquid volume was 3.0 L, the residence time was 166 hours, the circulating liquid temperature was 20° C., and the types of the raw material compounds were changed to those shown in the table below, to obtain fluorinated products of the raw material compounds.
The mass of the solvent CFE-419 was 2.33 times the mass of the raw material compound, and the pressure during fluorination was normal pressure.
In the table below, (1-2) means a compound represented by the following formula (1-2), (1-3) means a compound represented by the following formula (1-3), and (1-4) means a compound represented by the following formula (1-4), and the number of units in the formulas below is an average value.
The hydrogen residues and yields of the obtained fluorinated products are shown in Table 3. The number average molecular weights of the raw material compounds and the number average molecular weights of the obtained fluorinated products are also shown in Table 3.
The obtained fluorinated products were subjected to a heat resistance test in the same manner as in Examples 1-1 to 1-9 to evaluate their heat resistance. The results are also shown in Table 3.

As shown in Table 1, in Examples 1-1 to 1-7, 2-1 to 2-4, and 3-1 to 3-3, the target fluorine-containing compound was obtained in a higher yield than in Examples 1-8 to 1-9 and 2-5.

The disclosed method for producing a fluorine-containing compound can produce the target fluorine-containing compound in a higher yield than conventional methods. 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.). In addition, the obtained fluorine-containing compound and the derived 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 lubricant, an intermediate thereof, etc.

The disclosure of Japanese Patent Application No. 2022-185978, filed on November 21, 2022, is incorporated herein by reference in its entirety. All documents, patent applications, and technical standards described 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

A method for producing a fluorine-containing compound, comprising fluorinating an organic compound having at least one fluorinatable atom in a liquid containing the organic compound, thereby obtaining a fluorinated product having an average number of fluorinatable atoms per molecule of 0.01 or more.
The method for producing a fluorine-containing compound according to claim 1, wherein the average number of fluorinable atoms per molecule is 5 or less.
The method for producing a fluorine-containing compound according to claim 1 or 2, wherein the organic compound has a hydrogen atom as the fluorinatable atom.
The method for producing a fluorine-containing compound according to claim 1 or 2, wherein the organic compound is fluorinated by introducing a gas containing fluorine gas into the liquid.
The method for producing a fluorine-containing compound according to claim 1 or 2, wherein the liquid is retained in the reactor in which the fluorination is carried out for 200 hours or less.
The method for producing a fluorine-containing compound according to claim 1 or 2, wherein the liquid further contains a solvent.
The method for producing a fluorine-containing compound according to claim 6, wherein the mass of the solvent is 10 times or less the mass of the organic compound.
The method for producing a fluorine-containing compound according to claim 1 or 2, wherein the fluorination temperature is 5 to 50°C.
The method for producing a fluorine-containing compound according to claim 1 or 2, wherein the organic compound has a number average molecular weight of 800 to 28,000.
A fluorine-containing compound with an average number of hydrogen atoms per molecule of 0.01 to 5 and a number average molecular weight of 1,000 to 30,000.
The fluorine-containing compound according to claim 10, which contains a fluoropolyether chain.