Method for producing a composition containing a purified fluorine-containing ether compound

Abstract

To provide a method for producing a composition including a purified fluorine-containing ether compound.SOLUTION: A method for producing a composition including a purified fluorine-containing ether compound includes: (A) a process of obtaining a composition containing a fluorine-containing ether compound, an adduct of the nitrogen-containing compound expressed by general formula (11) to (13), and / or a fluorine-containing carboxylic acid analog, by reaction between a fluorine-containing olefin compound and a nitrogen-containing compound, in the presence of fluorine-containing ether compound, where the nitrogen-containing compound is a nitrogen-containing compound A having a structure in which an acyl group is bonded to a nitrogen atom, and / or a nitrogen-containing compound B being a tertiary amine compound; and (B) a process of separating the adduct of the nitrogen-containing compound and / or the fluorine-containing carboxylic acid analog from the composition obtained in the process (A).SELECTED DRAWING: None

Description

[Technical Field]

[0001] This disclosure relates to a method for producing a composition containing a purified fluorine-containing ether compound. [Background technology]

[0002] In recent years, hydrofluoroethers (HFEs) have attracted attention as a substitute for chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs) due to their low global warming potential (GWP) and ozone depletion potential (ODP), as well as their low toxicity.

[0003] Patent Document 1 discloses that by reacting a primary amine and / or a secondary amine with a composition containing a fluorine-containing ether and a fluorine-containing olefin, the fluorine-containing olefin can be converted into a high-boiling-point compound, and a purified fluorine-containing ether can be obtained by subsequent distillation purification. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2008-230981 [Overview of the project] [Problems that the invention aims to solve]

[0005] This disclosure relates to purified general formula (1) CHX 1 X 2 CF2OX 3 (In the formula, X 1 and X 2 X represents, either identically or differently, a hydrogen atom, a fluorine atom, or a trifluoromethyl group. 3 This represents an alkyl group which may contain fluorine atoms with 1 to 6 carbon atoms. However, X 1 and X 2Neither of them will be a trifluoromethyl group. ) It is an object of the present invention to provide a method for producing a composition containing a fluorine-containing ether compound represented by

Means for Solving the Problems

[0006] This disclosure includes the inventions described in the following items. Item 1. A method for producing a composition containing a purified fluorine-containing ether compound, comprising: The fluorine-containing ether compound has the general formula (1) CHX 1 X 2 CF2OX 3 (In the formula, X 1 and X 2 are the same or different and each represents a hydrogen atom, a fluorine atom, or a trifluoromethyl group, and X 3 represents an alkyl group which may contain a fluorine atom and has 1 to 6 carbon atoms. However, neither X 1 nor X 2 will be a trifluoromethyl group. ), and (A) In the presence of the fluorine-containing ether compound represented by the general formula (1) and water, chemistry Formula (2) CF 3 CF=CFOCH 3 and / or CF 2 =CFCF 2 OCH 3 represented by reacting a fluorine-containing olefin compound with a nitrogen-containing compound to convert the fluorine-containing olefin compound represented by the formula (2) into an adduct of the nitrogen-containing compound and a fluorine-containing carboxylic acid analog, thereby obtaining a composition containing the fluorine-containing ether compound represented by the general formula (1), the adduct of the nitrogen-containing compound, and the fluorine-containing carboxylic acid analog, wherein the nitrogen-containing compound is a nitrogen-containing compound A having a structure in which an acyl group is bonded to a nitrogen atom, and / or a nitrogen-containing compound B which is a tertiary amine compound; and chemistry (B) A step of separating the adduct of the nitrogen-containing compound and the fluorine-containing carboxylic acid analog from the composition obtained in the step (A) to obtain a composition containing the purified fluorine-containing ether compound. , at least one selected from the group consisting of amide compounds, urea compounds, urethane compounds and imide compounds A production method comprising the steps of including. term 2 In step (B), the composition obtained in step (A) is washed with water and distilled to separate the nitrogen-containing compound adduct and the fluorine-containing carboxylic acid analog from the composition obtained in step (A). 1 The manufacturing method described. term 3 The method for producing the compound according to item 1 or 2 above, wherein the fluorine-containing ether compound represented by the general formula (1) is 1,1,2,3,3,3-hexafluoropropyl methyl ether (HFE-356mec). term 4 A composition containing a fluorine-containing ether compound, The aforementioned fluorine-containing ether compound is general formula (1) CHX 1 X 2 CF2OX 3 (In the formula, X 1 and X 2 X represents, either identically or differently, a hydrogen atom, a fluorine atom, or a trifluoromethyl group. 3 This represents an alkyl group which may contain fluorine atoms with 1 to 6 carbon atoms. However, X 1 and X 2 Both of them cannot become trifluoromethyl groups. ) Represented as, The aforementioned composition, in the presence of water, chemistry Formula (2) CF 3 CF=CFOCH 3 and / or CF 2 =CFCF 2 OCH The product contains adducts and fluorine-containing carboxylic acid analogs of the nitrogen-containing compound, which are reaction products of the fluorine-containing olefin compound represented by 3 and the nitrogen-containing compound, wherein the nitrogen-containing compound has a structure in which an acyl group is bonded to a nitrogen atom. , at least one selected from the group consisting of amide compounds, urea compounds, urethane compounds and imide compounds Nitrogen-containing compound A, and / or nitrogen-containing compound B which is a tertiary amine compound, A composition in which the total content of the adduct of the nitrogen-containing compound and the fluorine-containing carboxylic acid analog is 5% by mass or less relative to the mass of the fluorine-containing ether compound. term 5 A composition containing a fluorine-containing ether compound, The aforementioned fluorine-containing ether compound is general formula (1) CHX 1X 2 CF2OX 3 (In the formula, X 1 and X 2 X represents, either identically or differently, a hydrogen atom, a fluorine atom, or a trifluoromethyl group. 3 This represents an alkyl group which may contain fluorine atoms with 1 to 6 carbon atoms. However, X 1 and X 2 Both of them cannot become trifluoromethyl groups. ) Represented as, The aforementioned composition, in the presence of water, chemistry Formula (2) CF 3 CF=CFOCH 3 and / or CF 2 =CFCF 2 OCH The product contains adducts and fluorine-containing carboxylic acid analogs of the nitrogen-containing compound, which are reaction products of the fluorine-containing olefin compound represented by 3 and the nitrogen-containing compound, wherein the nitrogen-containing compound has a structure in which an acyl group is bonded to a nitrogen atom. , at least one selected from the group consisting of amide compounds, urea compounds, urethane compounds and imide compounds Nitrogen-containing compound A, and / or nitrogen-containing compound B which is a tertiary amine compound, A composition in which the content of the adduct of the nitrogen-containing compound is 3% by mass or less relative to the mass of the fluorine-containing ether compound, and the content of the fluorine-containing carboxylic acid analog is 2% by mass or less relative to the mass of the fluorine-containing ether compound. term 6 A composition containing a fluorine-containing ether compound, The aforementioned fluorine-containing ether compound is 1,1,2,3,3,3-hexafluoropropyl methyl ether (HFE-356mec), The composition contains adducts and fluorine carboxylic acid analogs of a nitrogen-containing compound, which are reaction products of a fluorine-containing olefin compound represented as CF3CF=CFOCH3 and / or CF2=CFCF2OCH3 with a nitrogen-containing compound in the presence of water, wherein the nitrogen-containing compound has a structure in which an acyl group is bonded to a nitrogen atom. , at least one selected from the group consisting of amide compounds, urea compounds, urethane compounds and imide compounds Nitrogen-containing compound A, and / or nitrogen-containing compound B which is a tertiary amine compound, A composition in which the total content of the adduct of the nitrogen-containing compound and the fluorine-containing carboxylic acid analog is 5% by mass or less relative to the mass of the fluorine-containing ether compound. term 7 A composition containing a fluorine-containing ether compound, The aforementioned fluorine-containing ether compound is 1,1,2,3,3,3-hexafluoropropyl methyl ether (HFE-356mec), The composition contains adducts and fluorine carboxylic acid analogs of a nitrogen-containing compound, which are reaction products of a fluorine-containing olefin compound represented as CF3CF=CFOCH3 and / or CF2=CFCF2OCH3 with a nitrogen-containing compound in the presence of water, wherein the nitrogen-containing compound has a structure in which an acyl group is bonded to a nitrogen atom. , at least one selected from the group consisting of amide compounds, urea compounds, urethane compounds and imide compounds Nitrogen-containing compound A, and / or nitrogen-containing compound B which is a tertiary amine compound, A composition in which the content of the nitrogen-containing compound adduct is 3% by mass or less relative to the mass of the fluorine-containing ether, and the content of the fluorine-containing carboxylic acid analog is 2% by mass or less relative to the mass of the fluorine-containing olefin. term 8 A composition containing a fluorine-containing ether compound, The aforementioned fluorine-containing ether compound is general formula (1) CHX 1 X 2 CF2OX 3 (In the formula, X 1 and X 2 X represents, either identically or differently, a hydrogen atom, a fluorine atom, or a trifluoromethyl group. 3 This represents an alkyl group which may contain fluorine atoms with 1 to 6 carbon atoms. However, X 1 and X 2 Both of them cannot become trifluoromethyl groups. ) Represented as, The aforementioned composition, in the presence of water, chemistry Formula (2) CF 3 CF=CFOCH 3 and / or CF 2 =CFCF 2 OCH The product contains adducts and fluorine-containing carboxylic acid analogs of the nitrogen-containing compound, which are reaction products of the fluorine-containing olefin compound represented by 3 and the nitrogen-containing compound, wherein the nitrogen-containing compound has a structure in which an acyl group is bonded to a nitrogen atom. , at least one selected from the group consisting of amide compounds, urea compounds, urethane compounds and imide compoundsNitrogen-containing compound A, and / or nitrogen-containing compound B which is a tertiary amine compound, A composition in which the total content of the adduct of the nitrogen-containing compound and the fluorine-containing carboxylic acid analog is 0.2% by mass or less relative to the mass of the fluorine-containing ether compound. term 9 A composition containing a fluorine-containing ether compound, The aforementioned fluorine-containing ether compound is general formula (1) CHX 1 X 2 CF2OX 3 (In the formula, X 1 and X 2 X represents, either identically or differently, a hydrogen atom, a fluorine atom, or a trifluoromethyl group. 3 This represents an alkyl group which may contain fluorine atoms with 1 to 6 carbon atoms. However, X 1 and X 2 Both of them cannot become trifluoromethyl groups. ) Represented as, The aforementioned composition, in the presence of water, chemistry Formula (2) CF 3 CF=CFOCH 3 and / or CF 2 =CFCF 2 OCH The product contains adducts and fluorine-containing carboxylic acid analogs of the nitrogen-containing compound, which are reaction products of the fluorine-containing olefin compound represented by 3 and the nitrogen-containing compound, wherein the nitrogen-containing compound has a structure in which an acyl group is bonded to a nitrogen atom. , at least one selected from the group consisting of amide compounds, urea compounds, urethane compounds and imide compounds Nitrogen-containing compound A, and / or nitrogen-containing compound B which is a tertiary amine compound, A composition in which the content of the adduct of the nitrogen-containing compound is 0.1% by mass or less relative to the mass of the fluorine-containing ether compound, and the content of the fluorine-containing carboxylic acid analog is 0.1% by mass or less relative to the mass of the fluorine-containing ether compound. term 10 A composition containing a fluorine-containing ether compound, The aforementioned fluorine-containing ether compound is 1,1,2,3,3,3-hexafluoropropyl methyl ether (HFE-356mec), The composition contains adducts and fluorine carboxylic acid analogs of a nitrogen-containing compound, which are reaction products of a fluorine-containing olefin compound represented as CF3CF=CFOCH3 and / or CF2=CFCF2OCH3 with a nitrogen-containing compound in the presence of water, wherein the nitrogen-containing compound has a structure in which an acyl group is bonded to a nitrogen atom. , at least one selected from the group consisting of amide compounds, urea compounds, urethane compounds and imide compounds Nitrogen-containing compound A, and / or nitrogen-containing compound B which is a tertiary amine compound, A composition in which the total content of the adduct of the nitrogen-containing compound and the fluorine-containing carboxylic acid analog is 0.2% by mass or less relative to the mass of the fluorine-containing ether compound. term 11 A composition containing a fluorine-containing ether compound, The aforementioned fluorine-containing ether compound is 1,1,2,3,3,3-hexafluoropropyl methyl ether (HFE-356mec), The composition contains adducts and fluorine carboxylic acid analogs of a nitrogen-containing compound, which are reaction products of a fluorine-containing olefin compound represented as CF3CF=CFOCH3 and / or CF2=CFCF2OCH3 with a nitrogen-containing compound in the presence of water, wherein the nitrogen-containing compound has a structure in which an acyl group is bonded to a nitrogen atom. , at least one selected from the group consisting of amide compounds, urea compounds, urethane compounds and imide compounds Nitrogen-containing compound A, and / or nitrogen-containing compound B which is a tertiary amine compound, A composition in which the content of the nitrogen-containing compound adduct is 0.1% by mass or less relative to the mass of the fluorine-containing ether, and the content of the fluorine-containing carboxylic acid analog is 0.1% by mass or less relative to the mass of the fluorine-containing ether compound. [Effects of the Invention]

[0007] According to the manufacturing method of this disclosure, a composition containing a purified fluorine-containing ether compound represented by the above general formula (1) can be produced by a simple method. [Modes for carrying out the invention]

[0008] As a result of diligent research, the Disclosing Parties have found that the above objective can be achieved by utilizing the reaction between a fluorine-containing olefin compound represented by the above general formula (2) and a specific nitrogen-containing compound.

[0009] This disclosure is the result of further research based on the aforementioned findings. The embodiments included in this disclosure are described in detail below.

[0010] In this specification, the expressions “contains” and “includes” include the concepts of “contains,” “includes,” “substantially consists of,” and “consistes of only.”

[0011] In this specification, "purity" means the component ratio (mass %) determined by quantitative analysis using gas chromatography (GC).

[0012] In this specification, "reflux ratio" means the molar flow rate ratio (reflux / distillate) between reflux and distillate.

[0013] In this specification, "gauge pressure" refers to relative pressure with respect to atmospheric pressure, and means the pressure difference obtained by subtracting atmospheric pressure from absolute pressure. In this specification, gauge pressure is indicated with a "G," for example, MPaG. On the other hand, if the "G" is not included, it refers to absolute pressure.

[0014] In this specification, "A and / or B" means either A or B, or both A and B.

[0015] In this specification, "C1-C6 alkyl group" means methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, pentyl group, and hexyl group.

[0016] 1. Method for producing a composition containing a purified fluorine-containing ether compound The method for producing a composition containing the purified fluorine-containing ether compound of this disclosure (hereinafter also simply referred to as "the method of production of this disclosure") comprises the following steps (A) and (B) in this order. The method of production of this disclosure will be described below in the order of steps (A) and (B).

[0017] Process (A) Process (A) is general formula (1) CHX 1 X 2 CF2OX 3 (In the formula, X 1 and X 2 X represents, either identically or differently, a hydrogen atom, a fluorine atom, or a trifluoromethyl group. 3 This represents an alkyl group which may contain fluorine atoms with 1 to 6 carbon atoms. However, X 1 and X 2 Both cannot become trifluoromethyl groups. In the presence of a fluorine-containing ether compound represented by general formula (2)CX 1 X 2 =CF(CF2) n OX 3 (In the formula, n represents either 0 or 1. X 1 , X 2 and X 3 The same applies as above. However, X 1 or X 2 If is a trifluoromethyl group, then n is 0, and X 1 and X 2 The process involves a reaction between a fluorine-containing olefin compound represented by general formula (2) and a nitrogen-containing compound to convert the fluorine-containing olefin compound represented by general formula (2) into an adduct of the nitrogen-containing compound and / or a fluorine-containing carboxylic acid analog, thereby obtaining a composition comprising a fluorine-containing ether compound represented by general formula (1) and an adduct of the nitrogen-containing compound and / or a fluorine-containing carboxylic acid analog, wherein the nitrogen-containing compound is nitrogen-containing compound A having a structure in which an acyl group is bonded to a nitrogen atom, and / or nitrogen-containing compound B which is a tertiary amine compound.

[0018] In this disclosure, the fluorine-containing ether compound is the general formula (1) CHX1 X 2 CF2OX 3 (where X 1 , X 2 and X 3 are the same as above.) It is represented by. Specifically, CF3CHFCF2OX 3 , CHF2CF2OX 3 , CH2FCF2OX 3 , CH3CF2OX 3 etc. are exemplified (in each case, X 3 represents an alkyl group which may contain fluorine atoms and has 1 to 6 carbon atoms.).

[0019] The fluorine-containing ether compound represented by the general formula (1) is preferably at least one compound selected from the group consisting of CF3CHFCF2OCH3, CHF2CF2OCH3, CH2FCF2OCH3 and CH3CF2OCH3. Among these, CF3CHFCF2OCH3 (1,1,2,3,3,3-hexafluoropropyl methyl ether: HFE-356mec) is more preferable.

[0020] In the present disclosure, the fluorine-containing olefin compound is represented by the general formula (2) CX 1 X 2 =CF(CF2) n OX 3 (where X 1 , X 2 , X 3 and n are the same as above.) It is represented by. Specifically, CF3CF=CFOX 3 , CF2=CFCF2OX 3 , CF2=CFOX 3 , CHF=CFOX 3 , CH2=CFOX 3 etc. are exemplified (in each case, X 3 represents an alkyl group which may contain fluorine atoms and has 1 to 6 carbon atoms.).

[0021] The fluorine-containing olefin compound represented by general formula (2) is preferably at least one compound selected from the group consisting of CF3CF=CFOCH3, CF2=CFCF2OCH3, CF2=CFOCH3, CHF=CFOCH3, and CH2=CFOCH3. Of these, at least one of CF3CF=CFOCH3 and CF2=CFCF2OCH3 is more preferred.

[0022] In this disclosure, nitrogen-containing compound A, which has a structure in which an acyl group is bonded to a nitrogen atom, and / or nitrogen-containing compound B, which is a tertiary amine compound, are used as nitrogen-containing compounds to be reacted with a fluorine-containing olefin compound. Hereinafter, unless otherwise specified, the term nitrogen-containing compound refers collectively to "nitrogen-containing compound A and / or nitrogen-containing compound B".

[0023] Nitrogen-containing compound A (hereinafter also simply referred to as "nitrogen-containing compound A") having a structure in which an acyl group is bonded to a nitrogen atom can be defined as at least one selected from the group consisting of amide compounds, urea compounds, urethane compounds, and imide compounds having said structure. When these compounds are used in combination, examples of combinations include a mixture of an amide compound and a urea compound, a mixture of an amide compound and a urethane compound, a mixture of an amide compound and an imide compound, a mixture of a urea compound and a urethane compound, a mixture of a urea compound and an imide compound, and a mixture of a urethane compound and an imide compound.

[0024] In detail, each compound may be at least one selected from the group consisting of a chain-like amide compound represented by general formula (3), a cyclic amide compound represented by general formula (4), a chain-like urea compound represented by general formula (5), a cyclic urea compound represented by general formula (6), a chain-like urethane compound represented by general formula (7), a cyclic urethane compound represented by general formula (8), a chain-like imide compound represented by general formula (9), and a cyclic imide compound represented by general formula (10).

[0025] [ka] [In the formula, R1, R2, R3, R4, R6, R7, R8, R9, R 10 、R 12 、R 14 、R 15 、R 17 、R 19 and R 21 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent (among these, a hydrogen atom or an alkyl group having 1 to 3 carbon atoms which may have a substituent is preferred). R5 represents an alkyl group having 1 to 6 carbon atoms which may have a substituent (among these, an alkyl group having 1 to 3 carbon atoms which may have a substituent is preferred). R 11 、R 13 、R 16 、R 18 、R 20 and R 22 each independently represent an alkyl group having 1 to 6 carbon atoms which may have a substituent (among these, an alkyl group having 1 to 3 carbon atoms which may have a substituent is preferred). ]]

[0026] Specifically, examples of the amide compound include formamide, acetamide, N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), diethylacetamide, dipropylacetamide, dibutylacetamide, dimethylisobutylamide, dimethylpropylamide, 3-methoxy-N,N-dimethylpropionamide, N-methylpyrrolidone (NMP), N-ethylpyrrolidone, 2-pyrrolidone, N-methylpiperidone, benzamide, N-phenylacetamide, etc. There is no particular limitation to a chain structure or a cyclic structure, and they can be used. Among these amide compounds, N,N-dimethylformamide (DMF) or N,N-dimethylacetamide (DMAc) is preferred for reasons of easy availability, and N,N-dimethylformamide (DMF) is more preferred. The amide compounds can be used alone or in combination of two or more.

[0027] Examples of urea compounds include urea, 1,3-dimethylurea, tetramethylurea, 1,3-diethylurea, tetraethylurea, dipropylurea, tetrapropylurea, dibutylurea, tetrabutylurea, 1,3-dimethyl-2-imidazolidinone (DMI), 2-imidazolidinone, tetrahydro-2-pyrimididone, diphenylurea, and phenylurea. These compounds are not limited to linear or cyclic structures and can be used in any way. Among these urea compounds, tetramethylurea is preferred due to its availability. Urea compounds can be used individually or in combination of two or more.

[0028] Examples of urethane compounds include 2-azetidinone, 2-pyrrolidone, ethyl-N-methylcarbamate, 2-oxazolidone, 3-methyl-2-oxazolidone, methyl-N-phenylcarbamate, phenylurethane, methyl N-methylcarbamate, methyl carbamate, ethyl N-ethylcarbamate, ethyl carbamate, propyl N-propylcarbamate, propyl carbamate, butyl N-butylcarbamate, butyl carbamate, and phenyl carbamate. These compounds are not limited to linear or cyclic structures and can be used in any way. Among these urethane compounds, 2-pyrrolidone and 2-oxazolidone are preferred due to their availability, with 2-oxazolidone being more preferred. Each urethane compound can be used individually or in combination of two or more.

[0029] Examples of imide compounds include N-methyldiacetamide, diacetamide, N-methylsuccinimide, N-methylmaleimide, N-ethylsuccinimide, N-ethylmaleimide, N-acetyl-γ-caprolactam, N-methylphthalimide, N-phenylmaleimide, N-phenylsuccinimide, N-methylbis(trifluoroacetamide), N-methyl-N-(1-oxopropyl)propanamide, N-ethyl-N-(1-oxopropyl)propanamide, N-butyl-N-(1-oxopropyl)butanamide, N-(1-oxopropyl)propanamide, and N-(1-oxopropyl)butanamide, and they can be used without being limited to a chain or cyclic structure. Among these imide compounds, N-methyldiacetamide is preferred due to its availability. The imide compounds can be used individually or in combination of two or more.

[0030] Examples of nitrogen-containing compounds B (hereinafter also simply referred to as "nitrogen-containing compounds B"), which are tertiary amine compounds, include chain-like amine compounds, cyclic amine compounds, and heterocyclic aromatic compounds, and are not particularly limited to chain-like or cyclic structures. Specific examples of tertiary amine compounds include trimethylamine, triethylamine, tributylamine, diazabicycloundecene, N-methylpyrrolidine, pyridine, 4-dimethylaminopyridine, and N,N-dimethylbenzylamine. Among these amine compounds, triethylamine, diazabicycloundecene, and 4-dimethylaminopyridine are preferred due to their availability. Nitrogen-containing compounds B, which are tertiary amine compounds, can be used individually or in combination of two or more.

[0031] In this disclosure, the nitrogen-containing compound is preferably at least one selected from the group consisting of amide compounds, urea compounds, urethane compounds, imide compounds, and tertiary amine compounds. Specifically, the nitrogen-containing compound is preferably at least one selected from the group consisting of N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), 3-methoxy-N,N-dimethylpropionamide, N-methylpyrrolidone (NMP), urea, tetramethylurea, 1,3-dimethyl-2-imidazolidinone (DMI), 2-azetidinone, 2-pyrrolidone, ethyl-N-methylcarbamate, 3-methyl-2-oxazolidone, 2-oxazolidone, N-methyldiacetamide, N-methylsuccinimide, trimethylamine, triethylamine, diazabicycloundecene, N-methylpyrrolidine, pyridine, 4-dimethylaminopyridine, and N,N-dimethylbenzylamine.

[0032] The nitrogen-containing compounds usable in this disclosure can be identified by the Mulliken charge density on the nitrogen atom, specifically those having a Mulliken charge density of -0.65 or more and 0.1 or less on the nitrogen atom. While the Mulliken charge density on the nitrogen atom should be -0.65 or more and 0.1 or less, in the case of nitrogen-containing compound A, it is preferable that the Mulliken charge density on the nitrogen atom is -0.65 or more and 0 or less, more preferably -0.50 or more and 0 or less, and even more preferably -0.40 or more and 0 or less. In the case of nitrogen-containing compound B, it is preferable that the Mulliken charge density on the nitrogen atom is -0.50 or more and 0.1 or less, more preferably -0.50 or more and 0.1 or less, and even more preferably -0.40 or more and 0.1 or less. The Mulliken charge density in this disclosure is the charge density obtained by performing a structural optimization calculation using density functional theory (DFT) with Gaussian16 quantum chemistry calculation software from Gaussian, using B3LYP as the functional and 6-31G+(d) as the basis set.

[0033] As described above, nitrogen-containing compounds usable in this disclosure can be identified by the Mulliken charge density on the nitrogen atom, and can be identified as nitrogen-containing compounds with a Mulliken charge density on the nitrogen atom of -0.65 or more and 0.1 or less. Therefore, the method for producing a composition containing the purified fluorine-containing ether compound of this disclosure is A method for producing a composition containing a purified fluorine-containing ether compound, The aforementioned fluorine-containing ether compound is general formula (1) CHX 1 X 2 CF2OX 3 (In the formula, X 1 and X 2 X represents, either identically or differently, a hydrogen atom, a fluorine atom, or a trifluoromethyl group. 3 This represents an alkyl group which may contain fluorine atoms with 1 to 6 carbon atoms. However, X 1 and X 2 Both of them cannot become trifluoromethyl groups. ) Represented as, (A) In the presence of a fluorine-containing ether compound represented by the general formula (1), General formula (2)CX 1 X 2 =CF(CF2) n OX 3 (In the formula, n represents either 0 or 1. X 1 , X 2 and X 3 The same applies as above. However, X 1 or X 2 If is a trifluoromethyl group, then n is 0, and X 1 and X 2 The process involves a reaction between a fluorine-containing olefin compound represented by general formula (2) and a nitrogen-containing compound having a Mulliken charge density on the nitrogen atom of -0.65 or more and / or 0.1 or less, thereby converting the fluorine-containing olefin compound represented by general formula (2) into an adduct of the nitrogen-containing compound and / or a fluorine-containing carboxylic acid analog, thereby obtaining a composition containing the fluorine-containing ether compound represented by general formula (1) and the adduct of the nitrogen-containing compound and / or the fluorine-containing carboxylic acid analog; and (B) A method for production comprising the step of separating the adduct of the nitrogen-containing compound and / or the fluorine-containing carboxylic acid analog from the composition obtained in step (A) above to obtain a composition containing the purified fluorine-containing ether compound. It can also be written as follows.

[0034] In step (A), a fluorine-containing olefin compound represented by general formula (2) reacts with the nitrogen-containing compound in the presence of a fluorine-containing ether compound represented by general formula (1). The reaction between the fluorine-containing olefin compound represented by general formula (2) and the nitrogen-containing compound yields an adduct of the fluorine-containing olefin compound represented by general formula (2) and / or a carboxylic acid analog as a reaction product. As a result, step (A) yields a composition containing a fluorine-containing ether compound represented by general formula (1) and an adduct and / or a carboxylic acid analog of the nitrogen-containing compound.

[0035] Among the adducts of the nitrogen-containing compounds, the adducts when nitrogen-containing compound A is used as the nitrogen-containing compound are represented by general formulas (11) to (13).

[0036] [ka] [In the formula, X 1 and X 2 X represents, either identically or differently, a hydrogen atom, a fluorine atom, or a trifluoromethyl group. 3 This represents an alkyl group which may contain fluorine atoms with 1 to 6 carbon atoms. However, X 1 and X 2 Both R1 and R2 cannot be trifluoromethyl groups. R1 and R2 are the same or different alkyl groups having 1 to 6 carbon atoms, which may have a hydrogen atom or a substituent (of which alkyl groups having 1 to 3 carbon atoms, which may have a hydrogen atom or a substituent, are preferred).

[0037] For example, if the fluorine-containing olefin compound represented by general formula (2) is CF3CF=CFOCH3 and the nitrogen-containing compound is dimethylformamide (DMF), then CF3CHF-C(=O)-N(CH3)2 is obtained as an adduct. Also, if the fluorine-containing olefin compound represented by general formula (2) is CF2=CFCF2OCH3 and the nitrogen-containing compound is dimethylformamide (DMF), then N(CH3)2-C(=O)-CFCF2OCH3 is obtained as an adduct.

[0038] Furthermore, among the fluorinated carboxylic acid analogues, when nitrogen-containing compound A is used as the nitrogen-containing compound, the fluorinated carboxylic acid analogue is represented by general formulas (14) to (15).

[0039] [ka] [In the formula, X 1 and X 2 X represents, either identically or differently, a hydrogen atom, a fluorine atom, or a trifluoromethyl group. 3 This represents an alkyl group which may contain fluorine atoms with 1 to 6 carbon atoms. However, X 1 and X 2 Both of these cannot be trifluoromethyl groups. M represents Li, Na, or K.

[0040] For example, if the fluorine-containing olefin represented by general formula (2) is CF3CF=CFOCH3 and the nitrogen-containing compound is N,N-dimethylformamide (DMF), then CF3CFHCOOMe (Me=methyl group) and / or CF3CFHCOOM (M=Li, Na, or K) can be obtained as carboxylic acid analogs.

[0041] Furthermore, when nitrogen-containing compound B is used as the nitrogen-containing compound, the reaction product with the fluorine-containing olefin compound is mainly a fluorine-containing carboxylic acid analog, and a fluorine-containing carboxylic acid analog represented by general formulas (14) to (15) is obtained.

[0042] The content of the fluorine-containing olefin compound represented by general formula (2) before the reaction in step (A) is preferably 5% by mass or less relative to the fluorine-containing ether compound represented by general formula (1).

[0043] The reaction in step (A) is preferably a catalytic reaction between a fluorine-containing olefin compound represented by general formula (2) and the nitrogen-containing compound.

[0044] The amount of nitrogen-containing compound supplied is preferably 1 mole or more, more preferably 2 moles or more, preferably 50 moles or less, and even more preferably 40 moles or less, per mole of fluorine-containing olefin compound represented by general formula (2).

[0045] In the reaction of step (A), an inert gas component such as nitrogen gas may be present to suppress heat generation.

[0046] In the reaction of step (A), inorganic bases such as sodium hydroxide and potassium hydroxide may be present in the presence of the nitrogen-containing compound, from the viewpoint of reducing the amount of nitrogen-containing compound used. Furthermore, since step (A) may be carried out in the presence of water and inorganic bases, step (A) can be carried out continuously by adding the nitrogen-containing compound to the composition after the reaction shown in the following reaction formula (X).

[0047] Reaction formula (X) shows that a fluorine-containing olefin and an alcohol are reacted in the presence of water and inorganic salts to obtain a fluorine-containing ether compound and a fluorine-containing olefin compound. The resulting fluorine-containing ether compound corresponds to the fluorine-containing ether compound represented by general formula (1) in this disclosure, and the resulting fluorine-containing olefin compound corresponds to the fluorine-containing olefin compound represented by general formula (2) in this disclosure. Therefore, by adding the nitrogen-containing compound to the composition after reaction formula (X), step (A) of this disclosure can be carried out immediately following reaction formula (X). Furthermore, since the fluorine-containing carboxylic acid analog produced by the reaction of the fluorine-containing olefin compound, a product of reaction formula (X), with the nitrogen-containing compound selectively becomes a water-soluble fluorine-containing carboxylic acid salt, the purification load in the subsequent step (B) can also be reduced.

[0048] [ka] [In the formula, X 1 and X 2 X represents, either identically or differently, a hydrogen atom, a fluorine atom, or a trifluoromethyl group. 3 This represents an alkyl group which may contain fluorine atoms with 1 to 6 carbon atoms. However, X 1 and X 2 Neither of them can become a trifluoromethyl group.

[0049] Examples of inorganic bases that can be coexisted include sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, sodium bicarbonate, potassium bicarbonate, sodium carbonate, potassium carbonate, lithium carbonate, lithium phosphate, sodium phosphate, and potassium phosphate.

[0050] The equivalent amount of inorganic base used is preferably 0.1 equivalents or more, more preferably 0.2 equivalents or more, relative to the fluorine-containing ether compound represented by general formula (1). Furthermore, 1 equivalent or less is preferred, 0.75 equivalents or less is more preferred, and 0.5 equivalents or less is even more preferred.

[0051] The reaction in step (A) can be carried out in either the liquid or gas phase. In the case of carrying out the reaction in the liquid phase, one method is to introduce the nitrogen-containing compound into a crude liquid containing a fluorine-containing ether compound represented by general formula (1) and a fluorine-containing olefin compound represented by general formula (2) in a reactor, and then bring the crude liquid into contact with the nitrogen-containing compound. In the case of carrying out the reaction in the gas phase, one method is to bring the gasified crude liquid into contact with the nitrogen-containing compound in a reactor. From the viewpoint of improving the recovery rate of the fluorine-containing ether compound represented by general formula (1), it is preferable to carry out the reaction in step (A) in the liquid phase.

[0052] When the reaction in step (A) is carried out in the liquid phase, the reaction temperature is preferably 0°C or higher, preferably 100°C or lower, and more preferably 60°C or lower. The reaction pressure is preferably 0.0 MPaG or higher, preferably 0.5 MPaG or lower, and more preferably under atmospheric pressure. Furthermore, the reaction time is preferably 0.1 hours or higher, and more preferably 24 hours or lower.

[0053] When the reaction in step (A) is carried out in the gas phase, it is preferable to carry it out in the presence of a catalyst. Examples of catalysts include activated carbon, zeolite, alumina, silica-alumina, etc.

[0054] When the reaction in step (A) is carried out in the gas phase, the reaction temperature is preferably 70°C or higher and preferably 300°C or lower. The reaction pressure is preferably -0.05 MPaG or higher and preferably 1.00 PaG or lower. Furthermore, the reaction time is preferably 0.1 hours or more and preferably 24 hours or less.

[0055] Examples of reactors used in the liquid-phase reaction in process (A) include glass containers, glass-lined containers, resin-lined containers, and stainless steel containers. Examples of reactors used in the gas-phase reaction in process (A) include glass containers, glass-lined containers, resin-lined containers, and stainless steel containers.

[0056] Process (B) Step (B) is a step of separating the adduct of the nitrogen-containing compound and / or the fluorine-containing carboxylic acid analog from a composition comprising the fluorine-containing ether compound represented by general formula (1) obtained in step (A) and the adduct of the nitrogen-containing compound and / or the fluorine-containing carboxylic acid analog to obtain a composition comprising a purified fluorine-containing ether compound.

[0057] In a composition containing a purified fluorine-containing ether compound obtained through step (B), the purity of the fluorine-containing ether compound represented by general formula (1) is usually 95% by mass or more, preferably 97% by mass or more, more preferably 99% by mass or more, even more preferably 99.3% by mass or more, and particularly preferably 99.5% by mass or more.

[0058] In a composition containing a purified fluorine-containing ether compound obtained through step (B), the purity of the fluorine-containing olefin compound represented by general formula (2) is usually 0.1% by mass or less, preferably 0.05% by mass or less, more preferably 0.01% by mass or less, even more preferably 0.005% by mass or less, and particularly preferably 0.001% by mass or less.

[0059] The separation operation is preferably distillation, such as simple distillation, extractive distillation, pressure swing distillation, or thin-film distillation. Repeated distillation is also preferred. Distillation (especially rectification) can be performed using a distillation column (especially a rectification column) with multiple theoretical stages, and either continuous distillation or batch distillation may be employed. The pressure used for distillation (especially rectification) is preferably -0.05 MPaG or higher, and preferably 0.10 MPaG or lower. When distillation (especially rectification) is performed within this pressure range, the boiling point difference between the fluorine-containing ether compound represented by general formula (1), the fluorine-containing olefin compound represented by general formula (2), and the adduct of the nitrogen-containing compound and / or the fluorine-containing carboxylic acid analog can be increased (for example, a boiling point difference of 10°C or more can be achieved), thus improving the separation operation and separation accuracy.

[0060] The theoretical number of stages in a distillation column (especially a rectification column) used in distillation (especially rectification) is preferably two or more, and preferably 30 or less. The reflux ratio of a distillation column (especially a rectification column) used in distillation (especially rectification) is preferably 2 or more, and preferably 50 or less. The distillation column (especially a rectification column) is preferably made of a material resistant to corrosion, such as glass, stainless steel (SUS), Hastelloy, Inconel, or Monel, and more preferably made of SUS. Examples of packing materials used in a distillation column (especially a rectification column) include Raschig rings and McMahon packing.

[0061] According to the manufacturing method of the present disclosure, which includes steps (A) and (B) described above, purified general formula (1) CHX 1 X 2 CF2OX 3 (In the formula, X 1 and X 2 X represents, either identically or differently, a hydrogen atom, a fluorine atom, or a trifluoromethyl group. 3 This represents an alkyl group which may contain fluorine atoms with 1 to 6 carbon atoms. However, X 1 and X 2 Neither of them can become a trifluoromethyl group. A composition containing a fluorine-containing ether compound represented by ( ) is obtained.

[0062] 2. composition The compositions of this disclosure include two types: compositions obtained through step (A) in the manufacturing method of this disclosure (pre-purification compositions) and compositions obtained through steps (A) and (B) (post-purification compositions). Each of these will be described below.

[0063] Pre-purification composition The pre-purification composition of this disclosure is a composition comprising a fluorine-containing ether compound, The aforementioned fluorine-containing ether compound is general formula (1) CHX 1 X 2 CF2OX 3 (In the formula, X 1 and X 2X represents, either identically or differently, a hydrogen atom, a fluorine atom, or a trifluoromethyl group. 3 This represents an alkyl group which may contain fluorine atoms with 1 to 6 carbon atoms. However, X 1 and X 2 Both of them cannot become trifluoromethyl groups. ) Represented as, The aforementioned composition is general formula (2)CX 1 X 2 =CF(CF2) n OX 3 (In the formula, n represents either 0 or 1. X 1 , X 2 and X 3 The same applies as above. However, X 1 or X 2 If is a trifluoromethyl group, then n is 0, and X 1 and X 2 It is not possible for both to become trifluoromethyl groups.) The reaction product of a fluorine-containing olefin compound represented by and a nitrogen-containing compound contains an adduct of the nitrogen-containing compound and / or a fluorine-containing carboxylic acid analogue, wherein the nitrogen-containing compound is nitrogen-containing compound A having a structure in which an acyl group is bonded to a nitrogen atom, and / or nitrogen-containing compound B is a tertiary amine compound. The total content of the adduct of the nitrogen-containing compound and / or the fluorine-containing carboxylic acid analogue is 5% by mass or less relative to the mass (100% by mass) of the fluorine-containing ether compound. Note that the adduct of the nitrogen-containing compound and / or the fluorine-containing carboxylic acid analogue may be present individually, or both may be present, and the content of one of them may be substantially 0% by mass.

[0064] The total content of the nitrogen-containing compound adducts and / or fluorine-containing carboxylic acid analogs is preferably 4.5% by mass or less, and more preferably 4.0% by mass or less, based on the total mass (100% by mass) of the composition.

[0065] Here, if we specify the respective contents of the nitrogen-containing compound adducts and / or fluorine-containing carboxylic acid analogs separately, the pre-purification composition of this disclosure is a composition comprising a fluorine-containing ether compound, The aforementioned fluorine-containing ether compound is general formula (1) CHX 1 X 2 CF2OX 3 (In the formula, X 1 and X 2 X represents, either identically or differently, a hydrogen atom, a fluorine atom, or a trifluoromethyl group. 3 This represents an alkyl group which may contain fluorine atoms with 1 to 6 carbon atoms. However, X 1 and X 2 Both of them cannot become trifluoromethyl groups. ) Represented as, The aforementioned composition is general formula (2)CX 1 X 2 =CF(CF2) n OX 3 (In the formula, n represents either 0 or 1. X 1 , X 2 and X 3 The same applies as above. However, X 1 or X 2 If is a trifluoromethyl group, then n is 0, and X 1 and X 2 It is not possible for both to become trifluoromethyl groups.) The reaction product of a fluorine-containing olefin compound represented by and a nitrogen-containing compound contains an adduct of the nitrogen-containing compound and / or a fluorine-containing carboxylic acid analogue, wherein the nitrogen-containing compound is nitrogen-containing compound A having a structure in which an acyl group is bonded to a nitrogen atom, and / or nitrogen-containing compound B is a tertiary amine compound. The content of the adduct of the nitrogen-containing compound is 3% by mass or less relative to the mass (100% by mass) of the fluorine-containing ether compound, and the content of the fluorine-containing carboxylic acid analog is 2% by mass or less relative to the mass (100% by mass) of the fluorine-containing ether compound. Note that the adduct of the nitrogen-containing compound and the fluorine-containing carboxylic acid analog may be present individually, or both may be present, and the content of one may be substantially 0% by mass.

[0066] Furthermore, if the fluorine-containing ether compound represented by general formula (1) in the composition before purification is 1,1,2,3,3,3-hexafluoropropyl methyl ether (HFE-356mec) and the fluorine-containing olefin compound represented by general formula (2) is CF3CF=CFOCH3 and / or CF2=CFCF2OCH3, The pre-purification composition of this disclosure is a composition comprising a fluorine-containing ether compound, The aforementioned fluorine-containing ether compound is 1,1,2,3,3,3-hexafluoropropyl methyl ether (HFE-356mec), The composition contains an adduct of a nitrogen-containing compound and / or a fluorine-containing carboxylic acid analog, which are reaction products of a fluorine-containing olefin compound represented by CF3CF=CFOCH3 and / or CF2=CFCF2OCH3 with a nitrogen-containing compound, wherein the nitrogen-containing compound is nitrogen-containing compound A, which has a structure in which an acyl group is bonded to a nitrogen atom, and / or nitrogen-containing compound B, which is a tertiary amine compound. The total content of the adduct of the nitrogen-containing compound and / or the fluorine-containing carboxylic acid analogue is 5% by mass or less relative to the mass (100% by mass) of the fluorine-containing ether compound. Note that the adduct of the nitrogen-containing compound and / or the fluorine-containing carboxylic acid analogue may be present individually, or both may be present, and the content of one of them may be substantially 0% by mass.

[0067] Here, if we specify the respective contents of the nitrogen-containing compound adducts and / or fluorine-containing carboxylic acid analogs separately, the pre-purification composition of this disclosure is a composition comprising a fluorine-containing ether compound, The aforementioned fluorine-containing ether compound is 1,1,2,3,3,3-hexafluoropropyl methyl ether (HFE-356mec), The composition contains an adduct of a nitrogen-containing compound and / or a fluorine-containing carboxylic acid analog, which are reaction products of a fluorine-containing olefin compound represented by CF3CF=CFOCH3 and / or CF2=CFCF2OCH3 with a nitrogen-containing compound, wherein the nitrogen-containing compound is nitrogen-containing compound A, which has a structure in which an acyl group is bonded to a nitrogen atom, and / or nitrogen-containing compound B, which is a tertiary amine compound. The content of the nitrogen-containing compound adduct is 3% by mass or less relative to the mass (100% by mass) of the fluorine-containing ether, and the content of the fluorine-containing carboxylic acid analog is 2% by mass or less relative to the mass (100% by mass) of the fluorine-containing olefin. Note that the nitrogen-containing compound adduct and the fluorine-containing carboxylic acid analog may be present individually, or both, and the content of one may be substantially 0% by mass.

[0068] In the manufacturing method of the present disclosure, in step (A) in which a fluorine-containing olefin compound represented by general formula (2) is reacted with a specific nitrogen-containing compound (nitrogen-containing compound A and / or nitrogen-containing compound B) in the presence of a fluorine-containing ether compound represented by general formula (1) to convert the fluorine-containing olefin compound represented by general formula (2) into an adduct of the nitrogen-containing compound and / or a fluorine-containing carboxylic acid analog, the decomposition of the fluorine-containing ether compound represented by general formula (1) is suppressed. In the embodiment of the manufacturing method of the present disclosure in which nitrogen-containing compound B (tertiary amine compound) is used, even in the state of the pre-purification composition, the total content of the adduct of the nitrogen-containing compound and / or the fluorine-containing carboxylic acid analog is 5% by mass or less relative to the mass (100% by mass) of the fluorine-containing ether compound, which has the advantage of easily increasing the yield of the target product, the purified fluorine-containing ether compound.

[0069] Composition after purification The purified composition of this disclosure is a composition comprising a fluorine-containing ether compound, The aforementioned fluorine-containing ether compound is general formula (1) CHX 1 X 2 CF2OX 3 (In the formula, X 1 and X2 X represents, either identically or differently, a hydrogen atom, a fluorine atom, or a trifluoromethyl group. 3 This represents an alkyl group which may contain fluorine atoms with 1 to 6 carbon atoms. However, X 1 and X 2 Both of them cannot become trifluoromethyl groups. ) Represented as, The aforementioned composition is general formula (2)CX 1 X 2 =CF(CF2) n OX 3 (In the formula, n represents either 0 or 1. X 1 , X 2 and X 3 The same applies as above. However, X 1 or X 2 If is a trifluoromethyl group, then n is 0, and X 1 and X 2 It is not possible for both to become trifluoromethyl groups.) The reaction product of a fluorine-containing olefin compound represented by and a nitrogen-containing compound contains an adduct of the nitrogen-containing compound and / or a fluorine-containing carboxylic acid analogue, wherein the nitrogen-containing compound is nitrogen-containing compound A having a structure in which an acyl group is bonded to a nitrogen atom, and / or nitrogen-containing compound B is a tertiary amine compound. The total content of the adduct of the nitrogen-containing compound and / or the fluorine-containing carboxylic acid analogue is 0.2% by mass or less relative to the mass (100% by mass) of the fluorine-containing ether compound. Note that the adduct of the nitrogen-containing compound and / or the fluorine-containing carboxylic acid analogue may be present individually, or both may be present, and the content of one may be substantially 0% by mass.

[0070] As described above, nitrogen-containing compounds usable in this disclosure can be identified by the Mulliken charge density on the nitrogen atom, and can be identified as nitrogen-containing compounds with a Mulliken charge density on the nitrogen atom of -0.65 or more and 0.1 or less. Therefore, the purified composition of this disclosure is A composition containing a fluorine-containing ether compound, The aforementioned fluorine-containing ether compound is general formula (1) CHX 1 X 2 CF2OX3 (In the formula, X 1 and X 2 X represents, either identically or differently, a hydrogen atom, a fluorine atom, or a trifluoromethyl group. 3 This represents an alkyl group which may contain fluorine atoms with 1 to 6 carbon atoms. However, X 1 and X 2 Both of them cannot become trifluoromethyl groups. ) Represented as, The aforementioned composition is general formula (2)CX 1 X 2 =CF(CF2) n OX 3 (In the formula, n represents either 0 or 1. X 1 , X 2 and X 3 The same applies as above. However, X 1 or X 2 If is a trifluoromethyl group, then n is 0, and X 1 and X 2 It contains an adduct of a nitrogen-containing compound and / or a fluorine-containing carboxylic acid analogue, which is a reaction product of a fluorine-containing olefin compound represented by () and a nitrogen-containing compound having a Mulliken charge density on the nitrogen atom of -0.65 or more and 0.1 or less, A composition in which the total content of adducts and / or fluorine-containing carboxylic acid analogs of the nitrogen-containing compound is 0.2% by mass or less relative to the mass of the fluorine-containing ether compound. It can also be written as follows.

[0071] The total content of the nitrogen-containing compound adducts and / or fluorine-containing carboxylic acid analogs is preferably 0.2% by mass or less, and more preferably 0.1% by mass or less, based on the total mass (100% by mass) of the composition.

[0072] Here, if we specify the respective contents of the nitrogen-containing compound adducts and / or fluorine-containing carboxylic acid analogs separately, the pre-purification composition of this disclosure is a composition comprising a fluorine-containing ether compound, The aforementioned fluorine-containing ether compound is general formula (1) CHX 1 X 2 CF2OX3 (In the formula, X 1 and X 2 X represents, either identically or differently, a hydrogen atom, a fluorine atom, or a trifluoromethyl group. 3 This represents an alkyl group which may contain fluorine atoms with 1 to 6 carbon atoms. However, X 1 and X 2 Both of them cannot become trifluoromethyl groups. ) Represented as, The aforementioned composition is general formula (2)CX 1 X 2 =CF(CF2) n OX 3 (In the formula, n represents either 0 or 1. X 1 , X 2 and X 3 The same applies as above. However, X 1 or X 2 If is a trifluoromethyl group, then n is 0, and X 1 and X 2 It is not possible for both to become trifluoromethyl groups.) The reaction product of a fluorine-containing olefin compound represented by and a nitrogen-containing compound contains an adduct of the nitrogen-containing compound and / or a fluorine-containing carboxylic acid analogue, wherein the nitrogen-containing compound is nitrogen-containing compound A having a structure in which an acyl group is bonded to a nitrogen atom, and / or nitrogen-containing compound B is a tertiary amine compound. The content of the adduct of the nitrogen-containing compound is 0.1% by mass or less relative to the mass (100% by mass) of the fluorine-containing ether compound, and the content of the fluorine-containing carboxylic acid analog is 0.1% by mass or less relative to the mass (100% by mass) of the fluorine-containing ether compound. Note that the adduct of the nitrogen-containing compound and the fluorine-containing carboxylic acid analog may be present individually, or both may be present, and the content of one may be substantially 0% by mass.

[0073] Furthermore, in the above pre-purification composition, if the fluorine-containing ether compound represented by general formula (1) is 1,1,2,3,3,3-hexafluoropropyl methyl ether (HFE-356mec) and the fluorine-containing olefin compound represented by general formula (2) is CF3CF=CFOCH3 and / or CF2=CFCF2OCH3, The pre-purification composition of this disclosure is a composition comprising a fluorine-containing ether compound, The aforementioned fluorine-containing ether compound is 1,1,2,3,3,3-hexafluoropropyl methyl ether (HFE-356mec), The composition contains an adduct of a nitrogen-containing compound and / or a fluorine-containing carboxylic acid analog, which are reaction products of a fluorine-containing olefin compound represented by CF3CF=CFOCH3 and / or CF2=CFCF2OCH3 with a nitrogen-containing compound, wherein the nitrogen-containing compound is nitrogen-containing compound A, which has a structure in which an acyl group is bonded to a nitrogen atom, and / or nitrogen-containing compound B, which is a tertiary amine compound. The total content of the adduct of the nitrogen-containing compound and / or the fluorine-containing carboxylic acid analogue is 0.2% by mass or less relative to the mass (100% by mass) of the fluorine-containing ether compound. Note that the adduct of the nitrogen-containing compound and / or the fluorine-containing carboxylic acid analogue may be present individually, or both may be present, and the content of one may be substantially 0% by mass.

[0074] Here, if we specify the respective contents of the nitrogen-containing compound adducts and / or fluorine-containing carboxylic acid analogs separately, the pre-purification composition of this disclosure is a composition comprising a fluorine-containing ether compound, The aforementioned fluorine-containing ether compound is 1,1,2,3,3,3-hexafluoropropyl methyl ether (HFE-356mec), The composition contains an adduct of a nitrogen-containing compound and / or a fluorine-containing carboxylic acid analog, which are reaction products of a fluorine-containing olefin compound represented by CF3CF=CFOCH3 and / or CF2=CFCF2OCH3 with a nitrogen-containing compound, wherein the nitrogen-containing compound is nitrogen-containing compound A, which has a structure in which an acyl group is bonded to a nitrogen atom, and / or nitrogen-containing compound B, which is a tertiary amine compound. The content of the adduct of the nitrogen-containing compound is 0.1% by mass or less relative to the mass (100% by mass) of the fluorine-containing ether, and the content of the fluorine-containing carboxylic acid analog is 0.1% by mass or less relative to the mass (100% by mass) of the fluorine-containing ether compound. Note that the adduct of the nitrogen-containing compound and the fluorine-containing carboxylic acid analog may be present individually, or both may be present, and the content of one may be substantially 0% by mass.

[0075] In preferred embodiments, the purified composition of this disclosure contains HFE-356mec as an essential component as a purified fluorine-containing ether compound, and it is preferable that the purified fluorine-containing ether compound is HFE-356mec (consisting substantially only of HFE-356mec). The purified composition of this disclosure may or may not contain adducts and / or fluorine-containing carboxylic acid analogs of the nitrogen-containing compound other than the purified fluorine-containing ether compound. Here, not containing adducts and / or fluorine-containing carboxylic acid analogs of the nitrogen-containing compound means that the concentration is below the detection limit (ND) by quantitative analysis using gas chromatography (GC). In this case, the purified composition of this disclosure consists substantially only of HFE-356mec and is highly useful in that it yields HFE-356mec of higher purity than conventional methods. When the purified composition of this disclosure contains adducts and / or fluorinated carboxylic acid analogs of the nitrogen-containing compound, the total content of the adducts and / or fluorinated carboxylic acid analogs of the nitrogen-containing compound is preferably 0.1% by mass or less, more preferably 0.05% by mass or less, relative to the mass (100% by mass) of HFE-356mec. Furthermore, from the viewpoint of composition stability and cost reduction during the production of HFE-356mec, the total content of the adducts and / or fluorinated carboxylic acid analogs of the nitrogen-containing compound is preferably 0.005% by mass or more, more preferably 0.01% by mass or more, relative to the mass (100% by mass) of HFE-356mec.

[0076] The purified composition of the preferred embodiment of the present disclosure may contain hydrogen fluoride. If the purified composition of the preferred embodiment of the present disclosure contains hydrogen fluoride, the hydrogen fluoride content is preferably 0.01% by mass or less, more preferably 0.001% by mass or less, based on the mass (100% by mass) of HFE-356mec.

[0077] The uses of the purified composition of this disclosure are not limited, but it can be suitably used, for example, as a solvent, a solvent for coating agents, a solvent for lubricants, a solvent for fluorine oils, a reaction solvent, a solvent for extractants, a coating solution for organic EL, a heat transfer fluid, a refrigerant, a heat transfer fluid, a foaming agent, a fire extinguishing agent, a cleaning agent, a spinning solution, an electrolyte, an aerosol, a gas emulsion, or a solvent for electrophotographic equipment. [Examples]

[0078] Examples and comparative examples are shown below to provide a more detailed explanation of the embodiments of this disclosure. However, this disclosure is not limited to these examples. Hereinafter, "room temperature" means 20 to 25°C.

[0079] Example 1 (The nitrogen-containing compound is the chain-like amide compound of this disclosure) 182 g of crude material containing 94.4% by mass HFE-356mec, 1.38% by mass fluorine-containing olefin compounds [1.28% by mass CF3CF=CFOCH3 (olefin 1) and 0.10% by mass CF2=CFCF2OCH3 (olefin 2 (E,Z))], and 0.035% by mass hydrogen fluoride was placed in a 1 L glass container.

[0080] Next, 37 g of N,N-dimethylformamide, 100 g of water, and 17 g of potassium hydroxide were added, and the reaction was carried out at atmospheric pressure and 60°C for 5 hours. For N,N-dimethylformamide, the Mulliken charge was calculated by performing a structure optimization calculation using density functional theory (DFT) with B3LYP as the functional and 6-31G+(d) as the basis set, using Gaussian16 quantum chemistry calculation software from Gaussian Inc., and it was confirmed that the Mulliken charge on the nitrogen atom was -0.110.

[0081] Next, GC and 19F-NMR analysis were performed to confirm that the nitrogen-containing compound adduct was present in a proportion of 0.84% ​​by mass, and the fluorine-containing carboxylic acid analog was present in a proportion of 0.54% by mass. Both of these proportions are relative to the mass (100% by mass) of HFE-356mec (the same applies to the pre-purification composition below).

[0082] Subsequently, the fluorine ether layer and the aqueous layer were separated. The obtained fluorine ether layer was washed with water and then purified by rectification to obtain a fluoroether with a purity of 99.9% in yield of 93%. At this time, the adduct of nitrogen-containing compounds was ND, and the fluorine-containing carboxylic acid analog was ND. The content of these compounds is in proportion to the mass (100% by mass) of HFE-356mec (the same applies to the purified composition below).

[0083] Example 2 (where the nitrogen-containing compound is the chain-like amide compound of this disclosure) 182 g of crude material containing 94.4% by mass HFE-356mec, 1.38% by mass fluorine-containing olefin compounds [1.28% by mass CF3CF=CFOCH3 (olefin 1) and 0.10% by mass CF2=CFCF2OCH3 (olefin 2 (E,Z))], and 0.035% by mass hydrogen fluoride was placed in a 1 L glass container.

[0084] Next, 20 g of N,N-dimethylacetamide, 100 g of water, and 17 g of potassium hydroxide were added, and the reaction was carried out at atmospheric pressure and 40°C for 5 hours. For N,N-dimethylacetamide, the Mulliken charge was calculated by DFT (Dynamic Firmware Transform) as in Example 1, and it was confirmed that the Mulliken charge on the nitrogen atom was -0.217.

[0085] Next, GC and 19F-NMR analysis were performed to confirm that the nitrogen-containing compound adduct was present in 0.74% by mass and the fluorine-containing carboxylic acid analog was present in 0.64% by mass.

[0086] Subsequently, the fluorine ether layer and the aqueous layer were separated. The obtained fluorine ether layer was washed with water and then purified by rectification to obtain a fluoroether with a purity of 99.9% in yield of 94%. At this time, the adduct of the nitrogen-containing compound was ND, and the fluorine-containing carboxylic acid analog was ND.

[0087] Example 3 (where the nitrogen-containing compound is the chain-like amide compound of this disclosure) 182 g of crude material containing 94.4% by mass HFE-356mec, 1.38% by mass fluorine-containing olefin compounds [1.28% by mass CF3CF=CFOCH3 (olefin 1) and 0.10% by mass CF2=CFCF2OCH3 (olefin 2 (E,Z))], and 0.035% by mass hydrogen fluoride was placed in a 1 L glass container.

[0088] Next, 10 g of 3-methoxy-N,N-dimethylpropionamide, 50 g of water, and 17 g of sodium hydroxide were added, and the reaction was carried out at atmospheric pressure and room temperature for 24 hours. For 3-methoxy-N,N-dimethylpropionamide, structural optimization calculations were performed using DFT as in Example 1 to calculate the Mulliken charge, and it was confirmed that the Mulliken charge on the nitrogen atom was -0.224.

[0089] Next, GC and 19F-NMR analysis were performed to confirm that the nitrogen-containing compound adduct was present in a quantity of 0.70% by mass, and the fluorine-containing carboxylic acid analog was present in a quantity of 0.68% by mass.

[0090] Subsequently, the fluorine ether layer and the aqueous layer were separated. The obtained fluorine ether layer was washed with water and then purified by rectification to obtain a fluoroether with a purity of 99.9% in yield of 95%. At this time, the adduct of the nitrogen-containing compound was ND, and the fluorine-containing carboxylic acid analog was ND.

[0091] Example 4 (where the nitrogen-containing compound is the cyclic amide compound of the present disclosure) 182 g of crude material containing 94.4% by mass HFE-356mec, 1.38% by mass fluorine-containing olefin compounds [1.28% by mass CF3CF=CFOCH3 (olefin 1) and 0.10% by mass CF2=CFCF2OCH3 (olefin 2 (E,Z))], and 0.035% by mass hydrogen fluoride was placed in a 1 L glass container.

[0092] Next, 25 g of N-methylpyrrolidone, 50 g of water, and 15 g of potassium carbonate were added, and the reaction was carried out at atmospheric pressure and 40°C for 24 hours. For N-methylpyrrolidone, the Mulliken charge was calculated by DFT (Dynamic Fibre Transform) as in Example 1, and it was confirmed that the Mulliken charge on the nitrogen atom was -0.124.

[0093] Next, GC and 19F-NMR analysis were performed to confirm that the nitrogen-containing compound adduct was present in a quantity of 0.80% by mass, and the fluorine-containing carboxylic acid analog was present in a quantity of 0.58% by mass.

[0094] Subsequently, the fluorine ether layer and the aqueous layer were separated. The obtained fluorine ether layer was washed with water and then purified by rectification to obtain a fluoroether with a purity of 99.9% in yield of 91%. At this time, the adduct of the nitrogen-containing compound was ND, and the fluorine-containing carboxylic acid analog was ND.

[0095] Example 5 (Nitrogen-containing compound is the cyclic urethane compound of the present disclosure) 182 g of crude material containing 94.4% by mass HFE-356mec, 1.38% by mass fluorine-containing olefin compounds [1.28% by mass CF3CF=CFOCH3 (olefin 1) and 0.10% by mass CF2=CFCF2OCH3 (olefin 2 (E,Z))], and 0.035% by mass hydrogen fluoride was placed in a 1 L glass container.

[0096] Next, 25 g of 2-azetidinone, 50 g of water, and 30 g of sodium carbonate were added, and the reaction was carried out in the liquid phase at atmospheric pressure and 40°C for 24 hours. For 2-azetidinone, the Mulliken charge was calculated by DFT using structural optimization calculations, as in Example 1, and it was confirmed that the Mulliken charge on the nitrogen atom was -0.517.

[0097] Next, GC and 19F-NMR analysis were performed to confirm that the nitrogen-containing compound adduct was present in a quantity of 0.77% by mass, and the fluorine-containing carboxylic acid analog was present in a quantity of 0.61% by mass.

[0098] Subsequently, the fluorine ether layer and the aqueous layer were separated. The obtained fluorine ether layer was washed with water and then purified by rectification to obtain a fluoroether with a purity of 99.9% in yield of 91%. At this time, the adduct of the nitrogen-containing compound was ND, and the fluorine-containing carboxylic acid analog was ND.

[0099] Example 6 (Nitrogen-containing compound is the cyclic urethane compound of the present disclosure) 182 g of crude material containing 94.4% by mass HFE-356mec, 1.38% by mass fluorine-containing olefin compounds [1.28% by mass CF3CF=CFOCH3 (olefin 1) and 0.10% by mass CF2=CFCF2OCH3 (olefin 2 (E,Z))], and 0.035% by mass hydrogen fluoride was placed in a 1 L glass container.

[0100] Next, 25 g of 2-pyrrolidone, 50 g of water, and 17 g of potassium hydroxide were added, and the reaction was carried out in the liquid phase at atmospheric pressure and 40°C. For 2-pyrrolidone, the Mulliken charge was calculated by DFT (Dynamic Fibre Transform) as in Example 1, and it was confirmed that the Mulliken charge on the nitrogen atom was -0.496.

[0101] Next, GC and 19F-NMR analysis were performed to confirm that the nitrogen-containing compound adduct was present in a quantity of 0.87% by mass, and the fluorine-containing carboxylic acid analog was present in a quantity of 0.51% by mass.

[0102] Subsequently, the fluorine ether layer and the aqueous layer were separated. The obtained fluorine ether layer was washed with water and then purified by rectification to obtain a fluoroether with a purity of 99.9% in yield of 91%. At this time, the adduct of the nitrogen-containing compound was ND, and the fluorine-containing carboxylic acid analog was ND.

[0103] Example 7 (Nitrogen-containing compound is the chain-like urea compound of the present disclosure) 182 g of crude material containing 94.4% by mass HFE-356mec, 1.38% by mass fluorine-containing olefin compounds [1.28% by mass CF3CF=CFOCH3 (olefin 1) and 0.10% by mass CF2=CFCF2OCH3 (olefin 2 (E,Z))], and 0.035% by mass hydrogen fluoride was placed in a 1 L glass container.

[0104] Next, 35 g of tetramethylurea, 50 g of water, and 17 g of potassium hydroxide were added, and the reaction was carried out at atmospheric pressure and 40°C for 24 hours. For tetramethylurea, the Mulliken charge was calculated by performing a structural optimization calculation using DFT, as in Example 1, and it was confirmed that the Mulliken charge on the nitrogen atom was -0.256.

[0105] Next, GC and 19F-NMR analysis were performed to confirm that the nitrogen-containing compound adduct was present in a quantity of 0.77% by mass, and the fluorine-containing carboxylic acid analog was present in a quantity of 0.61% by mass.

[0106] Subsequently, the fluorine ether layer and the aqueous layer were separated. The obtained fluorine ether layer was washed with water and then purified by rectification to obtain a fluoroether with a purity of 99.9% in yield of 92%. At this time, the nitrogen-containing compound adduct was 0.03% by mass and the fluorine-containing carboxylic acid analog was 0.02% by mass.

[0107] Example 8 (Nitrogen-containing compound is a cyclic urea compound of the present disclosure) 182 g of crude material containing 94.4% by mass HFE-356mec, 1.38% by mass fluorine-containing olefin compounds [1.28% by mass CF3CF=CFOCH3 (olefin 1) and 0.10% by mass CF2=CFCF2OCH3 (olefin 2 (E,Z))], and 0.035% by mass hydrogen fluoride was placed in a 1 L glass container.

[0108] Next, 35 g of 1,3-dimethyl-2-imidazolidinone (DMI), 50 g of water, and 17 g of potassium hydroxide were added, and the reaction was carried out at atmospheric pressure and 60°C. For dimethylimidazolidinone, the Mulliken charge was calculated by DFT (Dynamic Firmware Transform) as in Example 1, and it was confirmed that the Mulliken charge on the nitrogen atom was -0.232.

[0109] Next, GC and 19F-NMR analysis were performed to confirm that the nitrogen-containing compound adduct was present in a quantity of 0.80% by mass, and the fluorine-containing carboxylic acid analog was present in a quantity of 0.58% by mass.

[0110] Subsequently, the fluorine ether layer and the aqueous layer were separated. The obtained fluorine ether layer was washed with water and then purified by rectification to obtain a fluoroether with a purity of 99.9% in yield of 91%. At this time, the nitrogen-containing compound adduct was 0.03% by mass and the fluorine-containing carboxylic acid analog was 0.03% by mass.

[0111] Example 9 (Nitrogen-containing compound is the chain-like urethane compound of the present disclosure) 182 g of crude material containing 94.4% by mass HFE-356mec, 1.38% by mass fluorine-containing olefin compounds [1.28% by mass CF3CF=CFOCH3 (olefin 1) and 0.10% by mass CF2=CFCF2OCH3 (olefin 2 (E,Z))], and 0.035% by mass hydrogen fluoride was placed in a 1 L glass container.

[0112] Next, 4 g of ethyl-N-methylcarbamate, 50 g of water, and 17 g of potassium hydroxide were added, and the reaction was carried out at atmospheric pressure and 60°C. For ethyl-N-methylcarbamate, the Mulliken charge was calculated by DFT (Dynamic Fibre Transform) as in Example 1, and it was confirmed that the Mulliken charge on the nitrogen atom was -0.612.

[0113] Next, GC and 19F-NMR analysis were performed to confirm that the nitrogen-containing compound adduct was present in a quantity of 0.75% by mass, and the fluorine-containing carboxylic acid analog was present in a quantity of 0.63% by mass.

[0114] Subsequently, the fluorine ether layer and the aqueous layer were separated. The obtained fluorine ether layer was washed with water and then purified by rectification to obtain a fluoroether with a purity of 99.9% in yield of 91%. At this time, the adduct of the nitrogen-containing compound was ND, and the fluorine-containing carboxylic acid analog was ND.

[0115] Example 10 (Nitrogen-containing compound is the cyclic urethane compound of the present disclosure) 182 g of crude material containing 94.4% by mass HFE-356mec, 1.38% by mass fluorine-containing olefin compounds [1.28% by mass CF3CF=CFOCH3 (olefin 1) and 0.10% by mass CF2=CFCF2OCH3 (olefin 2 (E,Z))], and 0.035% by mass hydrogen fluoride was placed in a 1 L glass container.

[0116] Next, 4 g of 3-methyl-2-oxazolidone, 250 g of water, and 50 g of potassium bicarbonate were added, and the reaction was carried out at atmospheric pressure and room temperature for 24 hours. For 3-methyl-2-oxazolidone, the Mulliken charge was calculated by DFT (Dynamic Fibre Transform) as in Example 1, and it was confirmed that the Mulliken charge on the nitrogen atom was -0.257.

[0117] Next, GC and 19F-NMR analysis were performed to confirm that the nitrogen-containing compound adduct was present in 0.72% by mass and the fluorine-containing carboxylic acid analog was present in 0.66% by mass.

[0118] Subsequently, the fluorine ether layer and the aqueous layer were separated. The obtained fluorine ether layer was washed with water and then purified by rectification to obtain a fluoroether with a purity of 99.9% in yield of 90%. At this time, the adduct of the nitrogen-containing compound was ND, and the fluorine-containing carboxylic acid analog was ND.

[0119] Example 11 (Nitrogen-containing compound is the chain-like imide compound of this disclosure) 182 g of crude material containing 94.4% by mass HFE-356mec, 1.38% by mass fluorine-containing olefin compounds [1.28% by mass CF3CF=CFOCH3 (olefin 1) and 0.10% by mass CF2=CFCF2OCH3 (olefin 2 (E,Z))], and 0.035% by mass hydrogen fluoride was placed in a 1 L glass container.

[0120] Next, 10 g of N-methyldiacetamide, 250 g of water, and 50 g of sodium bicarbonate were added, and the reaction was carried out at atmospheric pressure and room temperature for 24 hours. For N-methyldiacetamide, the Mulliken charge was calculated by DFT (Dynamic Fibre Transform) as in Example 1, and it was confirmed that the Mulliken charge on the nitrogen atom was -0.327.

[0121] Next, GC and 19F-NMR analysis were performed to confirm that the nitrogen-containing compound adduct was present in a quantity of 0.76% by mass, and the fluorine-containing carboxylic acid analog was present in a quantity of 0.62% by mass.

[0122] Subsequently, the fluorine ether layer and the aqueous layer were separated. The obtained fluorine ether layer was washed with water and then purified by rectification to obtain a fluoroether with a purity of 99.9% in yield of 90%. At this time, the adduct of the nitrogen-containing compound was ND, and the fluorine-containing carboxylic acid analog was ND.

[0123] Example 12 (Nitrogen-containing compound is a cyclic imide compound of the present disclosure) 182 g of crude material containing 94.4% by mass HFE-356mec, 1.38% by mass fluorine-containing olefin compounds [1.28% by mass CF3CF=CFOCH3 (olefin 1) and 0.10% by mass CF2=CFCF2OCH3 (olefin 2 (E,Z))], and 0.035% by mass hydrogen fluoride was placed in a 1 L glass container.

[0124] Next, 15 g of N-methylsuccinimide, 50 g of water, and 17 g of potassium hydroxide were added, and the reaction was carried out at atmospheric pressure and 60°C for 24 hours. For N-methylsuccinimide, the Mulliken charge was calculated by DFT using structural optimization calculations, as in Example 1, and it was confirmed that the Mulliken charge on the nitrogen atom was -0.197.

[0125] Next, GC and 19F-NMR analysis were performed to confirm that the nitrogen-containing compound adduct was present in a quantity of 0.80% by mass, and the fluorine-containing carboxylic acid analog was present in a quantity of 0.48% by mass.

[0126] Subsequently, the fluorine ether layer and the aqueous layer were separated. The obtained fluorine ether layer was washed with water and then purified by rectification to obtain a fluoroether with a purity of 99.9% in yield of 91%. At this time, the nitrogen-containing compound adduct was 0.05% by mass, and the fluorine-containing carboxylic acid analog was ND (non-degradable).

[0127] Example 13 (Nitrogen-containing compound is the chain-like amide compound of this disclosure) 182 g of crude material containing 94.4% by mass HFE-356mec, 1.38% by mass fluorine-containing olefin compounds [1.28% by mass CF3CF=CFOCH3 (olefin 1) and 0.10% by mass CF2=CFCF2OCH3 (olefin 2 (E,Z))], and 0.035% by mass hydrogen fluoride was placed in a 1 L glass container.

[0128] Next, 1 g of N,N-dimethylformamide, 50 g of water, and 17 g of potassium hydroxide were added, and the reaction was carried out at atmospheric pressure and 60°C for 24 hours. For N,N-dimethylformamide, the Mulliken charge was calculated by DFT (Dynamic Firmware Transform) as in Example 1, and it was confirmed that the Mulliken charge on the nitrogen atom was -0.347.

[0129] Next, GC and 19F-NMR analysis were performed to confirm that the nitrogen-containing compound adduct was 0.62% by mass and the fluorine-containing carboxylic acid analog was 0.76% by mass.

[0130] Subsequently, the fluorine ether layer and the aqueous layer were separated. The obtained fluorine ether layer was washed with water and then purified by rectification to obtain a fluoroether with a purity of 99.9% in yield of 91%. At this time, the adduct of the nitrogen-containing compound was ND, and the fluorine-containing carboxylic acid analog was ND.

[0131] Example 14 (Nitrogen-containing compound is the chain-like amine of the present disclosure) 182 g of crude material containing 94.4% by mass HFE-356mec, 1.38% by mass fluorine-containing olefin compounds [1.28% by mass CF3CF=CFOCH3 (olefin 1) and 0.10% by mass CF2=CFCF2OCH3 (olefin 2 (E,Z))], and 0.035% by mass hydrogen fluoride was placed in a 1 L glass container.

[0132] Next, 6 g of trimethylamine, 50 g of water, and 17 g of potassium hydroxide were added, and the reaction was carried out at atmospheric pressure and 60°C for 24 hours. For trimethylamine, the Mulliken charge was calculated by DFT (Dynamic Fracture Transform) as in Example 1, and it was confirmed that the Mulliken charge on the nitrogen atom was -0.168.

[0133] Next, GC and 19F-NMR analysis were performed to confirm that the nitrogen-containing compound adduct was ND and the fluorine-containing carboxylic acid analog was 1.25% by mass.

[0134] Subsequently, the fluorine ether layer and the aqueous layer were separated. The obtained fluorine ether layer was washed with water and then purified by rectification to obtain a fluoroether with a purity of 99.9% in yield of 86%. At this time, the adduct of the nitrogen-containing compound was ND, and the fluorine-containing carboxylic acid analog was ND.

[0135] Example 15 (Nitrogen-containing compound is the chain-like amine of the present disclosure) 182 g of crude material containing 94.4% by mass HFE-356mec, 1.38% by mass fluorine-containing olefin compounds [1.28% by mass CF3CF=CFOCH3 (olefin 1) and 0.10% by mass CF2=CFCF2OCH3 (olefin 2 (E,Z))], and 0.035% by mass hydrogen fluoride was placed in a 1 L glass container.

[0136] Next, 10 g of triethylamine, 50 g of water, and 17 g of potassium hydroxide were added, and the reaction was carried out at atmospheric pressure and 60°C for 24 hours. For triethylamine, the Mulliken charge was calculated by DFT (Dynamic Firmware Transform) as in Example 1, and it was confirmed that the Mulliken charge on the nitrogen atom was 0.041.

[0137] Next, GC and 19F-NMR analysis were performed to confirm that the nitrogen-containing compound adduct was ND and the fluorine-containing carboxylic acid analog was 1.17% by mass.

[0138] Subsequently, the fluorine ether layer and the aqueous layer were separated. The obtained fluorine ether layer was washed with water and then purified by rectification to obtain a fluoroether with a purity of 99.9% in yield of 86%. At this time, the adduct of the nitrogen-containing compound was ND, and the fluorine-containing carboxylic acid analog was ND.

[0139] Example 16 (Nitrogen-containing compound is a cyclic amine of the present disclosure) 182 g of crude material containing 94.4% by mass HFE-356mec, 1.38% by mass fluorine-containing olefin compounds [1.28% by mass CF3CF=CFOCH3 (olefin 1) and 0.10% by mass CF2=CFCF2OCH3 (olefin 2 (E,Z))], and 0.035% by mass hydrogen fluoride was placed in a 1 L glass container.

[0140] Next, 15 g of diazabicycloundecene (hereinafter referred to as DBU), 50 g of water, and 17 g of potassium hydroxide were added, and the reaction was carried out at atmospheric pressure and 60°C for 24 hours. For DBU, the Mulliken charge was calculated by performing a structural optimization calculation using DFT, as in Example 1, and it was confirmed that the Mulliken charge on the nitrogen atom was -0.255.

[0141] Next, GC and 19F-NMR analysis were performed to confirm that the nitrogen-containing compound adduct was ND and the fluorine-containing carboxylic acid analog was 0.84% ​​by mass.

[0142] Subsequently, the fluorine ether layer and the aqueous layer were separated. The obtained fluorine ether layer was washed with water and then purified by rectification to obtain a fluoroether with a purity of 99.9% in yield of 90%. At this time, the adduct of the nitrogen-containing compound was ND, and the fluorine-containing carboxylic acid analog was ND.

[0143] Example 17 (Nitrogen-containing compound is a cyclic amine of the present disclosure) 182 g of crude material containing 94.4% by mass HFE-356mec, 1.38% by mass fluorine-containing olefin compounds [1.28% by mass CF3CF=CFOCH3 (olefin 1) and 0.10% by mass CF2=CFCF2OCH3 (olefin 2 (E,Z))], and 0.035% by mass hydrogen fluoride was placed in a 1 L glass container.

[0144] Next, 9 g of N-methylpyrrolidine, 50 g of water, and 17 g of potassium hydroxide were added, and the reaction was carried out at 60 °C for 24 hours under normal pressure. For N-methylpyrrolidine, structural optimization calculations were performed by DFT in the same manner as in Example 1 to calculate the Mulliken charge, and it was confirmed that the Mulliken charge on the nitrogen atom was -0.127.

[0145] Next, GC and 19F-NMR analyses were performed, and it was confirmed that the nitrogen-containing compound adduct was N.D. and the fluorine-containing carboxylic acid analog was 0.99% by mass.

[0146] Thereafter, the fluorine ether layer and the aqueous layer were separated by liquid separation. The obtained fluorine ether layer was washed with water and then subjected to rectification purification to obtain fluoroether with a purity of 99.9% in a yield of 87%. At this time, the adduct of the nitrogen-containing compound was N.D., and the fluorine-containing carboxylic acid analog was N.D.

[0147] Example 18 (Nitrogen-containing compound is a heterocyclic aromatic compound of the present disclosure) 182 g of a crude product containing HFE-356mec with a purity of 94.4% by mass, a fluorine-containing olefin compound with a purity of 1.38% by mass [CF3CF=CFOCH3 (olefin 1) with a purity of 1.28% by mass and CF2=CFCF2OCH3 (olefin 2 (E,Z)) with a purity of 0.10% by mass], and hydrogen fluoride with a purity of 0.035% by mass was charged into a 1 L glass container.

[0148] Next, 8 g of pyridine, 50 g of water, and 17 g of potassium hydroxide were added, and the reaction was carried out at 60 °C for 24 hours under normal pressure. For pyridine, structural optimization calculations were performed by DFT in the same manner as in Example 1 to calculate the Mulliken charge, and it was confirmed that the Mulliken charge on the nitrogen atom was -0.179.

[0149] Next, GC and 19F-NMR analyses were performed, and it was confirmed that the nitrogen-containing compound adduct was N.D. and the fluorine-containing carboxylic acid analog was 1.05% by mass.

[0150] Thereafter, the fluorinated ether layer and the aqueous layer were separated by liquid separation. The obtained fluorinated ether layer was washed with water and then subjected to rectification purification to obtain fluoroether with a purity of 99.9% in a yield of 86%. At this time, the adduct of the nitrogen-containing compound was N.D., and the analog of the fluorinated carboxylic acid was N.D.

[0151] Example 19 (Nitrogen-containing compound is a heterocyclic aromatic compound of the present disclosure) A 1 L glass container was charged with 182 g of a crude product containing HFE-356mec with a purity of 94.4% by mass, a fluorinated olefin compound with a purity of 1.38% by mass [CF3CF=CFOCH3 (olefin 1) with a purity of 1.28% by mass and CF2=CFCF2OCH3 (olefin 2 (E,Z)) with a purity of 0.10% by mass], and hydrogen fluoride with a purity of 0.035% by mass.

[0152] Next, 12 g of 4-dimethylaminopyridine, 50 g of water, and 17 g of potassium hydroxide were added, and the reaction was carried out at normal pressure and 60 °C for 24 hours. Regarding 4-dimethylaminopyridine, the structural optimization calculation was performed by DFT in the same manner as in Example 1 to calculate the Mulliken charge, and it was confirmed that the Mulliken charge on the nitrogen atom was -0.210.

[0153] Next, GC and 19F-NMR analyses were performed, and it was confirmed that the adduct of the nitrogen-containing compound was N.D., and the analog of the fluorinated carboxylic acid was 0.89% by mass.

[0154] Thereafter, the fluorinated ether layer and the aqueous layer were separated by liquid separation. The obtained fluorinated ether layer was washed with water and then subjected to rectification purification to obtain fluoroether with a purity of 99.9% in a yield of 89%. At this time, the adduct of the nitrogen-containing compound was N.D., and the analog of the fluorinated carboxylic acid was N.D.

[0155] Example 20 (Nitrogen-containing compound is a cyclic amine of the present disclosure) 182 g of crude material containing 94.4% by mass HFE-356mec, 1.38% by mass fluorine-containing olefin compounds [1.28% by mass CF3CF=CFOCH3 (olefin 1) and 0.10% by mass CF2=CFCF2OCH3 (olefin 2 (E,Z))], and 0.035% by mass hydrogen fluoride was placed in a 1 L glass container.

[0156] Next, 14 g of N,N-dimethylbenzylamine, 50 g of water, and 17 g of potassium hydroxide were added, and the reaction was carried out at atmospheric pressure and 60°C for 24 hours. For dimethylbenzylamine, the Mulliken charge was calculated by DFT (Dynamic Firmware Analysis) as in Example 1, and it was confirmed that the Mulliken charge on the nitrogen atom was -0.100.

[0157] Next, GC and 19F-NMR analysis were performed to confirm that the nitrogen-containing compound adduct was ND and the fluorine-containing carboxylic acid analog was 0.95% by mass.

[0158] Subsequently, the fluorine ether layer and the aqueous layer were separated. The obtained fluorine ether layer was washed with water and then purified by rectification to obtain a fluoroether with a purity of 99.9% in yield of 88%. At this time, the adduct of the nitrogen-containing compound was ND, and the fluorine-containing carboxylic acid analog was ND.

[0159] Comparative Example 1 (The nitrogen-containing compound is amylamine (a primary amine and comparative product)) 182 g of crude material containing 94.4% by mass HFE-356mec, 1.38% by mass fluorine-containing olefin compounds [1.28% by mass CF3CF=CFOCH3 (olefin 1) and 0.10% by mass CF2=CFCF2OCH3 (olefin 2 (E,Z))], and 0.035% by mass hydrogen fluoride was placed in a 1 L glass container.

[0160] Next, 25 g of amylamine, 25 g of water, and 17 g of potassium hydroxide were added, and the reaction was carried out at atmospheric pressure and 40°C for 24 hours. For the amylamine, the Mulliken charge was calculated by performing a structural optimization calculation using DFT, as in Example 1, and it was confirmed that the Mulliken charge on the nitrogen atom was -0.821.

[0161] Subsequently, the fluorine ether layer and the aqueous layer were separated. The obtained fluorine ether layer was washed with water and then purified by rectification to obtain fluoroether with a purity of 99.8% in a yield of 79%.

[0162] Comparative Example 2 (The nitrogen-containing compound is benzylamine (a primary amine and comparative product)) 182 g of crude material containing 94.4% by mass HFE-356mec, 1.38% by mass fluorine-containing olefin compounds [1.28% by mass CF3CF=CFOCH3 (olefin 1) and 0.10% by mass CF2=CFCF2OCH3 (olefin 2 (E,Z))], and 0.035% by mass hydrogen fluoride was placed in a 1 L glass container.

[0163] Next, 25 g of benzylamine, 25 g of water, and 17 g of potassium hydroxide were added, and the reaction was carried out at atmospheric pressure and 40°C for 24 hours. For the benzylamine, the Mulliken charge was calculated by performing a structural optimization calculation using DFT, as in Example 1, and it was confirmed that the Mulliken charge on the nitrogen atom was -0.814.

[0164] Subsequently, the fluorine ether layer and the aqueous layer were separated. The obtained fluorine ether layer was washed with water and then purified by rectification to obtain fluoroether with a purity of 99.8% in yield of 80%.

Claims

1. A method for producing a composition containing a purified fluorine-containing ether compound, The fluorine-containing ether compound has the general formula (1) CHX １ X ２ CF ２ OX ３ (wherein X １ and X ２ are the same or different and each represents a hydrogen atom, a fluorine atom, or a trifluoromethyl group, and X ３ represents an alkyl group which may contain a fluorine atom and has 1 to 6 carbon atoms. However, both X １ and X ２ will not both be trifluoromethyl groups.) and is represented by (A) In the presence of a fluorine-containing ether compound represented by the general formula (1) and water, A step of obtaining a composition comprising a fluorine-containing olefin compound represented by the general formula (1), an adduct of the nitrogen-containing compound, and a fluorine-containing carboxylic acid analog, by reaction of a fluorine-containing olefin compound represented by the chemical formula (2) CF3 CF=CFOCH3 and / or CF2 =CFCF2OCH3 with a nitrogen-containing compound, wherein the nitrogen-containing compound is at least one nitrogen-containing compound A selected from the group consisting of amide compounds, urea compounds, urethane compounds, and imide compounds, and / or nitrogen-containing compound B which is a tertiary amine compound, wherein the nitrogen-containing compound is at least one nitrogen-containing compound A having a structure in which an acyl group is bonded to a nitrogen atom, and / or nitrogen-containing compound B which is a tertiary amine compound; and (B) A method for producing a composition comprising the step of separating the adduct of the nitrogen-containing compound and the fluorine-containing carboxylic acid analog from the composition obtained in step (A) above to obtain a composition containing the purified fluorine-containing ether compound.

2. The manufacturing method according to claim 1, wherein in step (B), the composition obtained in step (A) is washed with water and distilled to separate the nitrogen-containing compound adduct and the fluorine-containing carboxylic acid analog from the composition obtained in step (A).

3. The method for producing a fluorine-containing ether compound represented by the general formula (1) is 1,1,2,3,3,3-hexafluoropropyl methyl ether (HFE-356mec), according to claim 1 or 2.

4. A composition containing a fluorine-containing ether compound, The aforementioned fluorine-containing ether compound is general formula (1) CHX １ X ２ CF ２ OX ３ (In the formula, X １ and X ２ X represents, either identically or differently, a hydrogen atom, a fluorine atom, or a trifluoromethyl group. ３ This represents an alkyl group which may contain fluorine atoms having 1 to 6 carbon atoms. However, X １ and X ２ Both of them cannot become trifluoromethyl groups. ) Represented as, The composition contains an adduct of a nitrogen-containing compound and a fluorine-containing carboxylic acid analog, which are reaction products of a fluorine-containing olefin compound represented by the chemical formula (2) CF3 CF=CFOCH3 and / or CF2=CFCF2OCH3 with a nitrogen-containing compound in the presence of water, wherein the nitrogen-containing compound is at least one nitrogen-containing compound A selected from the group consisting of amide compounds, urea compounds, urethane compounds and imide compounds, and / or a tertiary amine compound B, having a structure in which an acyl group is bonded to a nitrogen atom. A composition in which the total content of the adduct of the nitrogen-containing compound and the fluorine-containing carboxylic acid analog is 5% by mass or less relative to the mass of the fluorine-containing ether compound.

5. A composition containing a fluorine-containing ether compound, The aforementioned fluorine-containing ether compound is general formula (1) CHX １ X ２ CF ２ OX ３ (In the formula, X １ and X ２ X represents, either identically or differently, a hydrogen atom, a fluorine atom, or a trifluoromethyl group. ３ This represents an alkyl group which may contain fluorine atoms having 1 to 6 carbon atoms. However, X １ and X ２ Both of them cannot become trifluoromethyl groups. ) Represented as, The composition contains an adduct of a nitrogen-containing compound and a fluorine-containing carboxylic acid analog, which are reaction products of a fluorine-containing olefin compound represented by the chemical formula (2) CF3 CF=CFOCH3 and / or CF2=CFCF2OCH3 with a nitrogen-containing compound in the presence of water, wherein the nitrogen-containing compound is at least one nitrogen-containing compound A selected from the group consisting of amide compounds, urea compounds, urethane compounds and imide compounds, and / or a tertiary amine compound B, having a structure in which an acyl group is bonded to a nitrogen atom. A composition in which the content of the nitrogen-containing compound adduct is 3% by mass or less relative to the mass of the fluorine-containing ether compound, and the content of the fluorine-containing carboxylic acid analog is 2% by mass or less relative to the mass of the fluorine-containing ether compound.

6. A composition containing a fluorine-containing ether compound, The fluorine-containing ether compound is 1,1,2,3,3,3-hexafluoropropyl methyl ether (HFE-356mec), The aforementioned composition, in the presence of water, CF ３ CF = CFOCH ３ and / or CF ２ = CFCF ２ OCH ３ The present invention contains a reaction product of a fluorine-containing olefin compound represented by and a nitrogen-containing compound, which includes an adduct of the nitrogen-containing compound and a fluorine-containing carboxylic acid analog, wherein the nitrogen-containing compound is at least one nitrogen-containing compound A selected from the group consisting of amide compounds, urea compounds, urethane compounds and imide compounds, and / or nitrogen-containing compound B which is a tertiary amine compound, having a structure in which an acyl group is bonded to a nitrogen atom. A composition in which the total content of the adduct of the nitrogen-containing compound and the fluorine-containing carboxylic acid analog is 5% by mass or less relative to the mass of the fluorine-containing ether compound.

7. A composition containing a fluorine-containing ether compound, The fluorine-containing ether compound is 1,1,2,3,3,3-hexafluoropropyl methyl ether (HFE-356mec), The aforementioned composition, in the presence of water, CF ３ CF = CFOCH ３ and / or CF ２ = CFCF ２ OCH ３ The present invention contains a reaction product of a fluorine-containing olefin compound represented by and a nitrogen-containing compound, which includes an adduct of the nitrogen-containing compound and a fluorine-containing carboxylic acid analog, wherein the nitrogen-containing compound is at least one nitrogen-containing compound A selected from the group consisting of amide compounds, urea compounds, urethane compounds and imide compounds, and / or nitrogen-containing compound B which is a tertiary amine compound, having a structure in which an acyl group is bonded to a nitrogen atom. A composition in which the content of the nitrogen-containing compound adduct is 3% by mass or less relative to the mass of the fluorine-containing ether, and the content of the fluorine-containing carboxylic acid analog is 2% by mass or less relative to the mass of the fluorine-containing olefin.

8. A composition containing a fluorine-containing ether compound, The aforementioned fluorine-containing ether compound is general formula (1) CHX １ X ２ CF ２ OX ３ (In the formula, X １ and X ２ X represents, either identically or differently, a hydrogen atom, a fluorine atom, or a trifluoromethyl group. ３ This represents an alkyl group which may contain fluorine atoms having 1 to 6 carbon atoms. However, X １ and X ２ Both of them cannot become trifluoromethyl groups. ) Represented as, The composition contains an adduct of a nitrogen-containing compound and a fluorine-containing carboxylic acid analog, which are reaction products of a fluorine-containing olefin compound represented by the chemical formula (2) CF3 CF=CFOCH3 and / or CF2=CFCF2OCH3 with a nitrogen-containing compound in the presence of water, wherein the nitrogen-containing compound is at least one nitrogen-containing compound A selected from the group consisting of amide compounds, urea compounds, urethane compounds and imide compounds, and / or a tertiary amine compound B, having a structure in which an acyl group is bonded to a nitrogen atom. A composition in which the total content of the adduct of the nitrogen-containing compound and the fluorine-containing carboxylic acid analog is 0.2% by mass or less relative to the mass of the fluorine-containing ether compound.

9. A composition containing a fluorine-containing ether compound, The aforementioned fluorine-containing ether compound is general formula (1) CHX １ X ２ CF ２ OX ３ (In the formula, X １ and X ２ X represents, either identically or differently, a hydrogen atom, a fluorine atom, or a trifluoromethyl group. ３ This represents an alkyl group which may contain fluorine atoms having 1 to 6 carbon atoms. However, X １ and X ２ Both of them cannot become trifluoromethyl groups. ) Represented as, The composition contains an adduct of a nitrogen-containing compound and a fluorine-containing carboxylic acid analog, which are reaction products of a fluorine-containing olefin compound represented by the chemical formula (2) CF3 CF=CFOCH3 and / or CF2=CFCF2OCH3 with a nitrogen-containing compound in the presence of water, wherein the nitrogen-containing compound is at least one nitrogen-containing compound A selected from the group consisting of amide compounds, urea compounds, urethane compounds and imide compounds, and / or a tertiary amine compound B, having a structure in which an acyl group is bonded to a nitrogen atom. A composition in which the content of the nitrogen-containing compound adduct is 0.1% by mass or less relative to the mass of the fluorine-containing ether compound, and the content of the fluorine-containing carboxylic acid analog is 0.1% by mass or less relative to the mass of the fluorine-containing ether compound.

10. A composition containing a fluorine-containing ether compound, The fluorine-containing ether compound is 1,1,2,3,3,3-hexafluoropropyl methyl ether (HFE-356mec), The aforementioned composition, in the presence of water, CF ３ CF = CFOCH ３ and / or CF ２ = CFCF ２ OCH ３ The present invention contains a reaction product of a fluorine-containing olefin compound represented by and a nitrogen-containing compound, which includes an adduct of the nitrogen-containing compound and a fluorine-containing carboxylic acid analog, wherein the nitrogen-containing compound is at least one nitrogen-containing compound A selected from the group consisting of amide compounds, urea compounds, urethane compounds and imide compounds, and / or nitrogen-containing compound B which is a tertiary amine compound, having a structure in which an acyl group is bonded to a nitrogen atom. A composition in which the total content of the adduct of the nitrogen-containing compound and the fluorine-containing carboxylic acid analog is 0.2% by mass or less relative to the mass of the fluorine-containing ether compound.

11. A composition containing a fluorine-containing ether compound, The fluorine-containing ether compound is 1,1,2,3,3,3-hexafluoropropyl methyl ether (HFE-356mec), The aforementioned composition, in the presence of water, CF ３ CF = CFOCH ３ and / or CF ２ = CFCF ２ OCH ３ The present invention contains a reaction product of a fluorine-containing olefin compound represented by and a nitrogen-containing compound, which includes an adduct of the nitrogen-containing compound and a fluorine-containing carboxylic acid analog, wherein the nitrogen-containing compound is at least one nitrogen-containing compound A selected from the group consisting of amide compounds, urea compounds, urethane compounds and imide compounds, and / or nitrogen-containing compound B which is a tertiary amine compound, having a structure in which an acyl group is bonded to a nitrogen atom. A composition in which the content of the nitrogen-containing compound adduct is 0.1% by mass or less relative to the mass of the fluorine-containing ether, and the content of the fluorine-containing carboxylic acid analog is 0.1% by mass or less relative to the mass of the fluorine-containing ether compound.

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