Method for producing a composition containing a purified fluorinated ether compound

Abstract

To provide a composition comprising a purified fluorine-containing ether compound.SOLUTION: A composition includes 1,1,2,3,3,3-hexafluoropropyl methyl ether (HFE-356 mec), and CF3CF=CFOCH3 and / or CF2=CFCF2OCH3. The total content of CF3CF=CFOCH3 and CF2=CFCF2OCH3 is 0.00001 mass% or more and 0.1 mass% or less relative to HFE-356 mec. In the composition, the purity of HFE-356 mec is more than 95 mass%.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present disclosure relates to a method for producing a composition containing a purified fluorinated ether compound. [Background technology]

[0002] In recent years, hydrofluoroethers (HFEs) have been increasingly used as hazardous substances due to their Global Warming Potential (GWP) and Ozone Depletion Potential (ODP). Because of its low depletion potential and low toxicity, it has been attracting attention as a substitute for chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs).

[0003] Non-Patent Document 1 discloses that 1,1,2,3,3,3-hexafluoropropyl methyl ether (HFE-356mec), which is a type of HFE, can be obtained by reacting hexafluoropropene (HFP) with methanol in the presence of an alkali. [Prior art documents] [Non-patent literature]

[0004] [Non-Patent Document 1] Green Chemistry, 2002, 4, 60-63 Summary of the Invention [Problem to be solved by the invention]

[0005] The present disclosure relates to a purified compound of general formula (1) CHX 1 X 2 CF 2 OX 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; X 3 represents an alkyl group having 1 to 6 carbon atoms. 1 and X2 and both of them cannot be trifluoromethyl groups. [Means for solving the problem]

[0006] The present disclosure includes the inventions described in the following sections. Section 1. A method for producing a composition containing a purified fluorinated ether compound, comprising the steps of: (A) General formula (1) CHX 1 X 2 CF 2 OX 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; X 3 represents an alkyl group having 1 to 6 carbon atoms. 1 and X 2 In the presence of a fluorine-containing ether compound represented by the formula (I), General formula (2)CX 1 X 2 =CF(CF 2 ) n OX 3 (In the formula, n represents 0 or 1. X 1 , X 2 and X 3 is the same as above, except that X 1 Or X 2 is a trifluoromethyl group, n is 0, and X 1 and X 2 (a) and (b) are not trifluoromethyl groups at the same time, and (b) are not trifluoromethyl groups at the same time, and (c) are not trifluoromethyl groups at the same time, and (d) are not trifluoromethyl groups at the same time, and (e) are not trifluoromethyl groups at the same time, and (f) are not trifluoromethyl groups at the same time, and (g ... (B) A production method comprising a step of separating the halogen adduct and / or oxide from the composition obtained in the step (A) to obtain a composition containing a purified fluorinated ether compound. Item 2. Item 2. The method according to item 1, wherein the halogenating agent is a chlorinating agent and / or a brominating agent. Section 3. Item 3. The method according to item 1 or 2, wherein in step (A), the reaction is carried out in a liquid phase. . Section 4. The method according to any one of items 1 to 3, wherein in the step (B), the composition obtained in the step (A) is rectified in a rectification column to separate the halogen adduct and / or oxide from the composition obtained in the step (A). Section 5. 5. The process according to any one of items 1 to 4, wherein the fluorine-containing ether compound represented by general formula (1) is 1,1,2,3,3,3-hexafluoropropyl methyl ether (HFE-356mec). Section 6. The fluorine-containing olefin compound represented by the general formula (2) is CF 3 CF=CFOCH 3 and / or CF 2 =CFCF 2 OCH 3 6. The method according to any one of items 1 to 5, wherein Section 7. 1,1,2,3,3,3-hexafluoropropyl methyl ether (HFE-356mec), CF 3 CF=CFOCH 3 and / or CF 2 =CFCF 2 OCH 3 and, A composition comprising: Section 8. CF 3 CF=CFOCH 3 and CF 2 =CFCF 2 OCH 3 The composition according to claim 7, wherein the total content of is 0.1 mass% or less based on HFE-356mec. Section 9. Further, it contains hydrogen fluoride, Item 9. The composition according to item 7 or 8, wherein the content of hydrogen fluoride is 0.01% by mass or less based on HFE-356mec. Effect of the Invention

[0007] According to the production method of the present disclosure, a composition containing a purified fluorinated ether compound represented by the above general formula (1) can be produced by a simple method. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0008] As a result of intensive research, the present inventors have found that the above object can be achieved by utilizing a reaction between a fluorine-containing olefin compound represented by the above general formula (2) and a halogenating agent and / or an oxidizing agent.

[0009] The present disclosure has been completed as a result of further research based on these findings. Hereinafter, embodiments included in the present disclosure will be described in detail.

[0010] In this specification, the expressions "contain" and "comprise" include the concepts of "contain", "include", "consist essentially of" and "consist only of".

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

[0012] In this specification, the term "reflux ratio" refers to the molar flow ratio of the reflux liquid to the distillate (reflux liquid / distillate).

[0013] Unless otherwise specified, pressures described in this specification are in units of gauge pressure, i.e., atmospheric pressure = 0.0 MPa.

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

[0015] In this specification, the term "alkyl group having 1 to 6 carbon atoms" refers to a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, and a hexyl group.

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

[0017] Process (A) In step (A), a compound represented by the general formula (1) CHX 1 X 2 CF 2 OX 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; X 3 represents an alkyl group having 1 to 6 carbon atoms. 1 and X 2 In the presence of a fluorine-containing ether compound represented by the general formula (2)CX 1 X 2 =CF(CF 2 ) n OX 3 (In the formula, n represents 0 or 1. X 1 and X 2 are the same or different and each represents a hydrogen atom, a fluorine atom, or a trifluoromethyl group; X 3 represents an alkyl group having 1 to 6 carbon atoms. 1 Or X 2 is a trifluoromethyl group, n is 0, and X 1 and X 2 and (b) a halogenating agent and / or an oxidizing agent, the fluorine-containing olefin compound represented by the formula (1) is reacted with a halogenating agent and / or an oxidizing agent to give This is a process in which the fluorine-containing olefin compound represented by the above general formula (2) is converted into a halogen adduct and / or oxide to obtain a composition containing the fluorine-containing ether compound represented by the above general formula (1) and the halogen adduct of the fluorine-containing olefin compound represented by the general formula (2) and / or the oxide of the fluorine-containing olefin compound represented by the general formula (2).

[0018] In the present disclosure, the fluorine-containing ether compound is represented by the general formula (1) CHX 1 X 2 CF 2 OX 3 (In the formula, X 1 , X 2 and X 3 is the same as above. ) Specifically, CF 3 CHFCF 2 OX 3 , CHF 2 CF 2 OX 3 , C.H. 2 FCF 2 OX 3 , C.H. 3 CF 2 OX 3 (All of these are X 3 represents an alkyl group having 1 to 6 carbon atoms).

[0019] The fluorine-containing ether compound represented by the general formula (1) is CF 3 CHFCF 2 OCH 3 , CHF 2 CF 2 OCH 3 , C.H. 2 FCF 2 OCH 3 and C.H. 3 CF 2 OCH 3 Of these, CF 3 CHFCF 2 OCH 3 (1,1,2,3,3,3-hexafluoropropyl methyl ether: HFE-356mec) is more preferred.

[0020] In the present disclosure, the fluorine-containing olefin compound is represented by the general formula (2)CX 1 X 2 =CF(CF 2 ) n OX 3 (In the formula, X 1 , X 2 , X 3 and n are the same as above.) Specifically, CF 3 CF=CFOX 3 , C.F. 2 =CFCF 2 OX 3 , C.F. 2 =CFOX 3 , CHF=CFOX 3 , C.H. 2 =CFOX 3 (All of these are X 3 represents an alkyl group having 1 to 6 carbon atoms).

[0021] The fluorine-containing olefin compound represented by the general formula (2) is CF 3 CF=CFOCH 3 , C.F. 2 =CFCF 2 OCH 3 , C.F. 2 =CFOCH 3 , CHF=CFOCH 3 and C.H. 2 =CFOCH 3 Of these, CF 3 CF=CFOCH 3 and CF 2 =CFCF 2 OCH 3 At least one of the above is more preferred.

[0022] The halogenating agent is preferably a chlorinating agent and / or a brominating agent.

[0023] Examples of the chlorinating agent include chlorine gas; hypochlorites such as sodium hypochlorite; chlorites such as sodium chlorite; chlorates such as sodium chlorate; and chlorine-containing interhalogen compounds. Examples of the chlorine-containing interhalogen compounds include chlorine monofluoride. Among these chlorinating agents, chlorine gas or sodium hypochlorite is preferred. The chlorinating agents can be used alone or in combination of two or more.

[0024] Examples of the brominating agent include bromine, bromates such as potassium bromate, and interhalogen compounds containing bromine. Examples of the interhalogen compounds containing bromine include bromine monofluoride. Among these brominating agents, bromine is preferred. The brominating agents can be used alone or in combination of two or more.

[0025] Examples of the oxidizing agent include hydrogen peroxide, oxygen, hypochlorites such as sodium hypochlorite, chlorites such as sodium chlorite, chlorates such as sodium chlorate, bromates such as sodium bromide and potassium bromide, etc. The oxidizing agents can be used alone or in combination of two or more.

[0026] Chlorine gas, hypochlorites such as sodium hypochlorite, chlorites such as sodium chlorite, and chlorates such as sodium chlorate can be used as chlorinating agents and oxidizing agents. Bromine and bromates such as potassium bromate can be used as brominating agents and oxidizing agents.

[0027] In step (A), the halogenating agent and / or oxidizing agent is more preferably at least one selected from the group consisting of chlorine gas, bromine and sodium hypochlorite.

[0028] In step (A), when a fluorine-containing olefin compound represented by general formula (2) reacts with a halogenating agent in the presence of a fluorine-containing ether compound represented by general formula (1), a halogen is added to the fluorine-containing olefin compound represented by general formula (2). As a result, a composition containing a fluorine-containing ether compound represented by general formula (1) and a halogen adduct of the fluorine-containing olefin compound represented by general formula (2) is obtained. In addition, in step (A), when a fluorine-containing olefin compound represented by general formula (2) reacts with an oxidizing agent in the presence of a fluorine-containing ether compound represented by general formula (1), the fluorine-containing olefin compound represented by general formula (2) is converted to an oxide. As a result, a composition containing a fluorine-containing ether compound represented by general formula (1) and an oxide of the fluorine-containing olefin compound represented by general formula (2) is obtained. Furthermore, in the step (A), when a fluorine-containing olefin compound represented by general formula (2), a halogenating agent and an oxidizing agent are reacted in the presence of a fluorine-containing ether compound represented by general formula (1), a composition containing the fluorine-containing ether compound represented by general formula (1), a halogen adduct of the fluorine-containing olefin compound represented by general formula (2), and an oxide of the fluorine-containing olefin compound represented by general formula (2) is obtained.

[0029] In step (A), when the fluorine-containing olefin compound represented by general formula (2) is converted into a halogen adduct and / or oxide by the reaction of the fluorine-containing olefin compound represented by general formula (2) with a halogenating agent and / or an oxidizing agent, it is preferable to make the fluorine-containing ether compound represented by general formula (1) and hydrogen fluoride coexist. In step (A), when the fluorine-containing ether compound represented by general formula (1) and hydrogen fluoride coexist, the amount of hydrogen fluoride is preferably 0.1 mass% or less, more preferably 0.075 mass% or less, and even more preferably 0.05 mass% or less, based on the fluorine-containing ether compound represented by general formula (1). In step (A), when the fluorine-containing ether compound represented by general formula (1) and hydrogen fluoride coexist, the amount of hydrogen fluoride is preferably 0.1 mass% or less, more preferably 0.075 mass% or less, and even more preferably 0.05 mass% or less, based on the fluorine-containing ether compound represented by general formula (1). The amount of the ether compound is preferably 0.0001% by mass or more, more preferably 0.0005% by mass or more, and even more preferably 0.001% by mass or more.

[0030] Examples of the halogen adduct include a chlorine adduct of the fluorine-containing olefin compound represented by general formula (2), a compound in which hydrogen contained in the fluorine-containing olefin compound represented by general formula (2) is replaced with chlorine or bromine, a bromine adduct of the fluorine-containing olefin compound represented by general formula (2), etc. Examples of the oxide include a compound in which the fluorine-containing olefin compound represented by general formula (2) is oxidized to a carboxylic acid, etc.

[0031] The content of the fluorine-containing olefin compound represented by general formula (2) before the reaction in step (A) is preferably 2 mass % or less based on the fluorine-containing ether compound represented by general formula (1).

[0032] The reaction in step (A) is preferably a contact reaction between a fluorine-containing olefin compound represented by general formula (2) and a halogenating agent and / or an oxidizing agent.

[0033] The amount of the halogenating agent to be supplied is preferably 1 mole or more and preferably 2 moles or less per mole of the fluorine-containing olefin compound represented by general formula (2). The amount of the oxidizing agent to be supplied is preferably 1 mole or more and preferably 2 moles or less per mole of the fluorine-containing olefin compound represented by general formula (2).

[0034] In the reaction of step (A), an inert gas component such as nitrogen gas may be allowed to coexist in order to suppress heat generation.

[0035] The reaction in step (A) can be carried out in a liquid phase or a gas phase. When the reaction is carried out in a liquid phase, a method in which a halogenating agent and / or an oxidizing agent is introduced into a crude liquid containing a fluorinated ether compound represented by general formula (1) and a fluorinated olefin compound represented by general formula (2) in a reactor, and the crude liquid is contacted with the halogenating agent and / or the oxidizing agent can be mentioned. When the reaction is carried out in a gas phase, a method in which a gasified crude liquid is contacted with a halogenating agent and / or an oxidizing agent in a reactor can be mentioned. From the viewpoint of improving the recovery rate of the fluorinated ether compound represented by general formula (1), the reaction in step (A) is preferably carried out in a liquid phase.

[0036] When the reaction in step (A) is carried out in a liquid phase, it is preferable to bring the fluorine-containing olefin compound represented by general formula (2) into contact with the halogenating agent and / or oxidizing agent by irradiating light in the presence of the fluorine-containing ether compound represented by general formula (1). As a light source for irradiating light, it is preferable to use a light source capable of irradiating ultraviolet light having a wavelength of about 300 nm or more and 400 nm or less. Specific examples include arc lamps containing mercury, argon or xenon, and filament lamps containing tungsten and halogen. The halogenating agent and / or oxidizing agent may be continuously supplied under light irradiation, or a predetermined amount may be introduced into the reactor all at once and then light irradiation may be started.

[0037] When the reaction in step (A) is carried out in a liquid phase, the reaction temperature is preferably 0° C. or higher, and preferably 30° C. or lower, and more preferably lower than 20° C. The reaction pressure is preferably 0.0 MPa or higher, and preferably 0.5 MPa or lower, and more preferably atmospheric pressure. The reaction time is preferably 0.1 hours or higher, and preferably 24 hours or shorter.

[0038] When the reaction in step (A) is carried out in a gas phase, it is preferably carried out in the presence of a catalyst, such as activated carbon, zeolite, alumina, or silica-alumina.

[0039] When the reaction in step (A) is carried out in a gas phase, the reaction temperature is preferably 70° C. or higher and 300° C. or lower. The reaction pressure is preferably −0.05 MPa or higher and 0.50 MPa or lower. Furthermore, the reaction time is preferably 0.1 hours or higher and 24 hours or lower.

[0040] The reactor used in the liquid phase reaction in step (A) may be a glass vessel, a glass-lined vessel, a resin-lined vessel, a stainless steel vessel, or the like. The reactor used in the gas phase reaction in step (A) may be a glass vessel, a glass-lined vessel, a resin-lined vessel, a stainless steel vessel, or the like.

[0041] Process (B) Step (B) is a step of separating the halogen adduct of the fluorine-containing olefin compound represented by general formula (2) and / or the oxide of the fluorine-containing olefin compound represented by general formula (2) from a composition containing the fluorine-containing ether compound represented by general formula (1) obtained in step (A) and the halogen adduct of the fluorine-containing olefin compound represented by general formula (2) and / or the oxide of the fluorine-containing olefin compound represented by general formula (2) to obtain a composition containing a purified fluorine-containing ether compound represented by general formula (1).

[0042] In the composition obtained through step (B), the purity of the fluorinated ether compound represented by general formula (1) is usually more than 95 mass%, preferably 97 mass% or more, more preferably 99 mass% or more, even more preferably 99.3 mass% or more, and particularly preferably 99.5 mass% or more.

[0043] In the composition obtained through step (B), the purity of the fluorine-containing olefin compound represented by general formula (2) is usually 0.1 mass% or less, preferably 0.05 mass% or less, more preferably 0.01 mass% or less, even more preferably 0.005 mass% or less, and particularly preferably 0.001 mass% or less.

[0044] As the separation operation, distillation (particularly preferably rectification) is preferably adopted. For the distillation (particularly rectification), a distillation column (particularly a rectification column) having a large number of theoretical plates can be used, and either continuous distillation or batch distillation may be adopted. The pressure for carrying out the distillation (particularly rectification) is preferably -0.05 MPa or more, and preferably 0.10 MPa or less. When the distillation (particularly rectification) is carried out within such a pressure range, the boiling point difference between the fluorine-containing ether compound represented by the general formula (1) and the fluorine-containing olefin compound halogen adduct represented by the general formula (2) and / or the fluorine-containing olefin compound oxide represented by the general formula (2) can be increased (for example, the boiling point difference can be made 10°C or more), thereby improving the separation operation and separation accuracy.

[0045] The number of theoretical plates of a distillation column (particularly a rectification column) used in distillation (particularly rectification) is preferably 2 or more and preferably 30 or less. The reflux ratio of a distillation column (particularly a rectification column) used in distillation (particularly rectification) is preferably 2 or more and preferably 50 or less. The distillation column (particularly a rectification column) is preferably made of a material resistant to corrosion such as glass, stainless steel (SUS), HASTALLOY, INCONEL, MONEL, etc., and is more preferably made of SUS. Examples of packing materials used in a distillation column (particularly a rectification column) include Raschig rings and McMahon packings.

[0046] According to the production method of the present disclosure including the above steps (A) and (B), a purified compound represented by the general formula (1) CHX 1 X 2 CF 2 OX 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; X 3 represents an alkyl group having 1 to 6 carbon atoms. 1 and X 2 Both of these cannot be trifluoromethyl groups. A composition containing a fluorinated ether compound can be obtained.

[0047] 2. composition The composition of the present disclosure contains 1,1,2,3,3,3-hexafluoropropyl methyl ether (HFE-356mec) as an essential component, and further contains CF 3 CF=CFOCH 3 and CF 2 =CFCF 2 OCH 3 In the present disclosure, HFE-356mec and CF 3 CF=CFOCH 3 and / or CF 2 =CFCF 2 OCH 3 The composition comprising the compound can be used as a cleaning agent.

[0048] The compositions of the present disclosure include HFE-356mec, CF 3 CF=CFOCH 3 and CF 2 =CFCF 2 OCH 3 In this case, it is preferable to use CF 3 CF=CFOCH 3 and CF 2 =CFCF 2 OCH 3 The total content of CF is preferably 0.1% by mass or less, more preferably 0.05% by mass or less, and even more preferably 0.01% by mass or less, based on HFE-356mec. In addition, from the viewpoints of the stability of the composition, cost reduction during the production of HFE-356mec, etc., 3 CF=CFOCH 3 and CF 2 =CFCF 2 OCH 3 The total content of is preferably 0.00001% by mass or more, more preferably 0.00005% by mass or more, and even more preferably 0.0001% by mass or more, based on HFE-356mec.

[0049] The composition of the present disclosure may contain hydrogen fluoride. When the composition of the present disclosure contains hydrogen fluoride, the content of hydrogen fluoride is preferably 0.01% by mass or less, more preferably 0.001% by mass or less, based on HFE-356mec.

[0050] The composition of the present disclosure may contain a trace amount of water. The water content in the composition of the present disclosure is 3 CF=CFOCH 3 and / or CF 2 =CFCF 2 OCH 3 The amount of moisture is preferably 0.3 mass % or less, and more preferably 0.05 mass % or less, based on the total amount of. When the composition of the present disclosure contains a small amount of moisture, decomposition of the fluorine-containing olefin compound is suppressed, and the stability of the composition is improved. EXAMPLES

[0051] The following examples are provided to more specifically describe the embodiments of the present disclosure. However, the present disclosure is not limited to these examples. Hereinafter, "room temperature" refers to 20 to 25°C.

[0052] (Example 1-1: Liquid-phase catalytic reaction using chlorine gas) In a 1 L glass container, HFE-356mec with a purity of 94.4 mass%, a fluorine-containing olefin compound with a purity of 1.38 mass% (CF 3 CF=CFOCH 3 and CF with a purity of 0.10% by mass 2 =CFCF 2 OCH 3) and 300 g of crude material containing hydrogen fluoride with a purity of 0.035% by mass were charged. Next, while cooling the glass vessel to 0°C, chlorine gas was supplied at 20 ml / min for 30 minutes, and the contact reaction between the fluorine-containing olefin compound in the crude material and the chlorine gas was carried out in the liquid phase at a pressure of 0.0 MPa. Then, 25 g of a 10% by mass aqueous sodium sulfite solution was added and stirred for 30 minutes, and after confirming the disappearance of the chlorine gas with potassium iodide starch paper, the organic phase was separated. The separated organic phase was washed with water to obtain 246 g of a composition containing HFE-356mec (purity 95.5% by mass) (purity of HFE-356mec 95.5% by mass, recovery rate of HFE-356mec 82%).

[0053] (Example 1-2: Rectification in a rectification column) A 500 mL glass vessel was equipped with a glass rectification column (theoretical number of plates: 5) using a SUS packing, a condenser (temperature of the cooling water in the condenser: 0°C to 5°C), and a fractionator. 220 g of the composition containing HFE-356mec (246 g) obtained in Example 1-1 was added to the apparatus, and a total reflux state was maintained for 1 hour. Thereafter, the reflux ratio was Fractional distillation was started from 50, and was completed when 177 g of a fraction was collected. The obtained fraction was analyzed by GC, and it was confirmed that the purity of HFE-356mec was 99.9 mass% (recovery rate 80%) and the purity of the fluorine-containing olefin compound was 0.002 mass%. The purity of hydrogen fluoride was 0.0002 mass%. In addition, the GC analysis of the obtained fraction did not confirm the presence of a chlorine adduct of the fluorine-containing olefin compound and an oxide of the fluorine-containing olefin compound.

[0054] (Example 1-3: Liquid-phase catalytic reaction using chlorine gas) In a 1 L SUS container, HFE-356mec with a purity of 93.0 mass%, a fluorine-containing olefin compound with a purity of 1.84 mass% (CF 3 CF=CFOCH 3 and CF with a purity of 0.10% by mass 2 =CFCF 2 OCH 3) and 300 g of crude material containing hydrogen fluoride with a purity of 0.035% by mass were charged. Then, under room temperature conditions, chlorine gas was supplied at 173 ml / min for 10 minutes, and the contact reaction between the fluorine-containing olefin compound in the crude material and the chlorine gas was carried out in the liquid phase at a pressure of 0.3 MPa. Then, 25 g of a 10% by mass aqueous sodium sulfite solution was added and stirred for 30 minutes, and after confirming with potassium iodide starch paper that the chlorine gas had disappeared, the organic phase was separated. The separated organic phase was washed with water to obtain 285 g of a composition containing HFE-356mec (purity of HFE-356mec: 94.5% by mass, recovery rate of HFE-356mec: 96.5%).

[0055] (Example 1-4: Gas-phase catalytic reaction using chlorine gas) In a 1 L SUS container, HFE-356mec with a purity of 93.0 mass%, a fluorine-containing olefin compound with a purity of 1.84 mass% (CF 3 CF=CFOCH 3 and CF with a purity of 0.10% by mass 2 =CFCF 2 OCH 3 ) and 300 g of crude material containing hydrogen fluoride with a purity of 0.035% by mass were charged. The reactor was heated to 70°C, and chlorine gas was supplied at 173 ml / min for 10 minutes, and the contact reaction between the fluorine-containing olefin compound in the crude material and the chlorine gas was carried out in the gas phase at a pressure of 0.4 MPa. Then, 25 g of a 10% by mass aqueous sodium sulfite solution was added and stirred for 30 minutes, and after confirming the disappearance of the chlorine gas with potassium iodide starch paper, the organic phase was separated. The separated organic phase was washed with water to obtain 282 g of a composition containing HFE-356mec (purity of HFE-356mec 94.2% by mass, recovery rate of HFE-356mec 95.2%).

[0056] (Example 1-5: Rectification in a rectification column) A 500 mL glass vessel was equipped with a glass rectification column (5 theoretical plates) using a SUS packing, a condenser (temperature of cooling water in the condenser: 0°C to 5°C), and a fractionator. 220 g of the composition (261 g) containing HFE-356mec obtained in Example 1-3 was added to the apparatus, and a total reflux state was maintained for 1 hour. Thereafter, fractional distillation was started from a reflux ratio of 50, and the fractional distillation was completed when 99 g of a fraction was recovered. The obtained fraction was analyzed by GC, and it was confirmed that the purity of HFE-356mec was 99.9 mass% (recovery rate 45%) and the purity of the fluorine-containing olefin compound was 0.003 mass%. The purity of hydrogen fluoride was 0.0002 mass%. In addition, the GC analysis of the obtained fraction did not confirm the presence of a chlorine adduct of the fluorine-containing olefin compound and an oxide of the fluorine-containing olefin compound.

[0057] (Example 2-1: Liquid phase catalytic reaction using sodium hypochlorite) In a 1 L glass container, HFE-356mec with a purity of 94.4 mass%, a fluorine-containing olefin compound with a purity of 1.37 mass% (CF 3 CF=CFOCH 3 and CF with a purity of 0.10% by mass 2 =CFCF 2 OCH 3 220 g of the crude product containing fluorine-containing olefin compound and hydrogen fluoride with a purity of 0.035% by mass, and 66 g of a 12% by mass aqueous sodium hypochlorite solution were charged. The mixture was then stirred under reflux at 54° C. for 1.5 hours, and the contact reaction between the fluorine-containing olefin compound in the crude product and sodium hypochlorite was carried out in the liquid phase at a pressure of 0.0 MPa. Even after 1.5 hours from the addition, GC confirmed that the fluorine-containing olefin compound remained (purity 0.474 mass%). Next, 33 g of 12 mass% sodium hypochlorite aqueous solution was added every hour for a total of three times (total of 99 g added), but GC confirmed that the fluorine-containing olefin compound remained (purity 0.07 mass%), so the mixture was returned to room temperature and stirred for 16 hours. Then, 15.5 g of 10 mass% sodium sulfite aqueous solution was added and stirred for 30 minutes, and after confirming that the sodium hypochlorite had disappeared with potassium iodide starch paper, the organic phase was separated. The separated organic phase was washed with water to obtain 186 g of a composition containing HFE-356mec (purity of HFE-356mec 95.7 mass%, recovery rate of HFE-356mec 85%).

[0058] (Example 2-2: Liquid phase catalytic reaction using sodium hypochlorite) In a 1 L glass container, HFE-356mec with a purity of 94.4 mass%, a fluorine-containing olefin compound with a purity of 1.37 mass% (CF 3 CF=CFOCH 3 and CF with a purity of 0.10% by mass 2 =CFCF 2 OCH 3 ) and 220 g of a crude material containing hydrogen fluoride with a purity of 0.035% by mass, and 66 g of a 12% by mass aqueous sodium hypochlorite solution were charged. Then, the mixture was stirred at room temperature for 22 hours, and a contact reaction between the fluorine-containing olefin compound in the crude material and sodium hypochlorite was carried out in the liquid phase at a pressure of 0.0 MPa. Then, 15.5 g of a 10% by mass aqueous sodium sulfite solution was added and stirred for 30 minutes, and after confirming with potassium iodide starch paper that sodium hypochlorite had disappeared, the organic phase was separated. The separated organic phase was washed with water to obtain 183 g of a composition containing HFE-356mec (yield of HFE-356mec: 83%).

[0059] (Example 2-3: Rectification in a rectification column) A 500 mL glass vessel was equipped with a rectification column (5 theoretical plates) using SUS packing, a condenser (temperature of cooling water in the condenser: 0°C to 5°C), and a fractionator, and 90 g of the composition (183 g) containing HFE-356mec obtained in Example 2-2 was added and the total reflux state was maintained for 1 hour. Thereafter, fractional distillation was started from a reflux ratio of 50, and the fractional distillation was completed when 71 g of a fraction was recovered. The obtained fraction was analyzed by GC, and it was confirmed that the purity of HFE-356mec was 99.9 mass% (recovery rate 79%) and the purity of the fluorine-containing olefin compound was 0.003 mass%. The purity of hydrogen fluoride was 0.0002 mass%. In addition, the GC analysis of the obtained fraction did not confirm the presence of a chlorine adduct of the fluorine-containing olefin compound and an oxide of the fluorine-containing olefin compound.

[0060] (Example 2-4: Rectification in a rectification column) A 500 mL glass vessel was equipped with a rectification column (theoretical plate number 2) using a SUS packing, a condenser (temperature of cooling water in the condenser: 0°C to 5°C), and a fractionator, and 90 g of the composition (183 g) containing HFE-356mec obtained in Example 2-2 was added and the total reflux state was maintained for 1 hour. Thereafter, fractional distillation was started from a reflux ratio of 50, and the fractional distillation was completed when 69 g of a fraction was recovered. The obtained fraction was analyzed by GC, and it was confirmed that the purity of HFE-356mec was 99.8 mass% (recovery rate 76%) and the purity of the fluorine-containing olefin compound was 0.003 mass%. The purity of hydrogen fluoride was 0.0002 mass%. In addition, the GC analysis of the obtained fraction did not confirm the presence of a chlorine adduct of the fluorine-containing olefin compound and an oxide of the fluorine-containing olefin compound.

[0061] (Example 3-1: Liquid-phase catalytic reaction using bromine) In a 5 L reactor, HFE-356mec having a purity of 93% by mass and a fluorine-containing olefin compound having a purity of 1.38% (CF 3 CF=CFOCH 3 and CF with a purity of 0.10% by mass 2 =CFCF 2 OCH3 ) and 2918 g of a crude material containing hydrogen fluoride with a purity of 0.025% by mass. The reactor was then placed in an ice bath to cool the inside temperature to 5° C. or less, and 133 g of bromine was added dropwise to the reactor. After the dropwise addition was completed, the inside of the reactor was returned to room temperature and the mixture was stirred at room temperature for 10 hours to carry out a contact reaction between the fluorine-containing olefin compound in the crude material and bromine in a liquid phase. , and was carried out. Next, the obtained reaction liquid was transferred to a 5L plastic bucket, and 500g of ice water and 50g of sodium bicarbonate were added and stirred. After confirming that it was basic with pH test paper, sodium thiosulfate (40g) was added. Then, potassium iodide starch paper was used to confirm that excess bromine had been removed. Next, the reaction liquid was transferred to a separatory funnel and the lower layer was removed, and the product was a colorless and transparent liquid. Mass analysis of the product was carried out by gas chromatography / mass spectrometry (GC / MS), and structural analysis was carried out by NMR spectroscopy. From the results of mass analysis and structural analysis, it was confirmed that the purity of HFE-356mec was 96.1% by mass, and the recovery rate of HFE-356mec was 96% (yield 2793g).

[0062] (Example 3-2: Rectification in a rectification column) The product obtained in Example 3-1 was transferred to a 3 L round-bottom flask equipped with a mantle heater and an internal thermometer in advance, and a glass Oldershaw-type rectification column (theoretical plate number 20) equipped with a condenser and a fractionator was attached to the top of the round-bottom flask. The mantle heater was set to 100°C, and a total reflux state was maintained for 1 hour. Thereafter, fractional distillation was started from a reflux ratio of 50, and purification was terminated when 2725 g of a fraction was collected. The obtained fraction was subjected to mass analysis by GC / MS, and structural analysis was performed by NMR spectrum. From the results of mass analysis and structural analysis, the recovery rate of HFE-356mec was calculated from Example 3-1 to be 93%, and the purity of HFE-356mec was 99.95% by mass. The purity of the fluorine-containing olefin compound was 0.003% by mass. In addition, the GC analysis of the obtained fraction did not confirm the presence of a bromine adduct of the fluorine-containing olefin compound and an oxide of the fluorine-containing olefin compound.

[0063] Example 4 In a glass flask equipped with a Dimroth condenser, HFE-356mec, CF 3 CF=CFOCH 3 and solvents containing hydrogen fluoride (CF 3 CF=CFOCH 3 The content of hydrogen fluoride was 0.004% by mass relative to HFE-356mec, and the content of hydrogen fluoride was 0.0002% by mass relative to HFE-356mec. Furthermore, test pieces of iron, copper, zinc, and aluminum were placed in the flask, and the solution was heated to 53°C in air under atmospheric pressure and refluxed to observe the stability of the solvent and each test piece. After 72 hours, no acid was generated in the solvent, and no changes such as corrosion were observed in any of the test pieces.

[0064] Example 5 CF 3 CF=CFOCH 3 The observation was carried out under the same conditions as in Example 4, except that the content of was 0.004 mass% relative to HFE-356mec and 0.3 mass% of water was added to the solvent. After 72 hours, no acid was generated in the solvent, and no changes such as corrosion were observed in any of the test pieces.

[0065] Example 6 CF 3 CF=CFOCH 3 The observation was carried out under the same conditions as in Example 4, except that the content of was 0.009 mass% relative to HFE-356mec, the content of hydrogen fluoride was 0.0004 mass% relative to HFE-356mec, and 0.03 mass% of water was added to the solvent. After 72 hours, no acid was generated in the solvent, and no changes such as corrosion were observed in any of the test pieces.

[0066] Comparative Example 1 In a glass flask equipped with a Dimroth condenser, HFE-356mec, CF 3 CF=CFOCH 3 , C.F. 2 CF=CF 2 OCH 3 and solvents containing hydrogen fluoride (CF 3 CF=CFOCH 3The content of is 1.38% by mass for HFE-356mec, and CF 2 CF=CF 2 OCH 3 The content of hydrogen fluoride was 0.8% by mass relative to HFE-356mec, and the content of hydrogen fluoride was 0.0004% by mass relative to HFE-356mec. The flask was then filled with iron, copper, zinc, and aluminum test pieces, which were then heated to 53°C in air at atmospheric pressure and refluxed to observe the stability of the solvent and each test piece. After 72 hours, acid was generated in the solvent, and corrosion was observed in all test pieces.

Claims

[Claim 1] 1,1,2,3,3,3-hexafluoropropyl methyl ether (HFE-356mec), CF ３ CF = CFOCH ３ and / or C.F. ２ =CFCF ２ OCH ３ and, Hydrogen fluoride, Water, A composition comprising: CF ３ CF = CFOCH ３ and C.F. ２ =CFCF ２ OCH ３ The total content of is 0.00001% by mass or more and 0.1% by mass or less relative to HFE-356mec, In the composition, the purity of HFE-356mec is greater than 95% by mass; The content of the hydrogen fluoride is 0.01% by mass or less relative to HFE-356mec, The composition, wherein the content of the water is 0.3 mass % or less based on the total amount of HFE-356mec and CF 3 CF═CFOCH 3 and / or CF 2 ═CFCF 2 OCH 3 .