Method for producing perfluoroalkene compounds and compositions

Abstract

The present invention provides a method for producing a perfluoroalkene compound, which enables the production of the perfluoroalkene compound in high yield, and a composition having a high content of the perfluoroalkene compound. [Solution] A method for producing a perfluoroalkene compound represented by the following formula 1, comprising a step of reacting a raw material perfluoroalkene compound with a perfluoroalkyl iodide in the presence of a fluorinated aluminum chloride-containing catalyst to obtain the perfluoroalkene compound represented by formula 1, wherein the fluorinated aluminum chloride-containing catalyst is obtained by removing at least a portion of by-products from a product obtained by reacting aluminum chloride in the presence of a hydrochlorofluorocarbon. TIFF0007799217000020.tif32114

Description

[Technical Field]

[0001] FIELD OF THE DISCLOSURE The present disclosure relates to methods for making perfluoroalkene compounds and compositions. [Background technology]

[0002] Perfluoroalkyne compounds have traditionally been used in semiconductor dry etching gases, various refrigerants, foaming agents, heat transfer media, and the like. A method using a perfluoroalkene compound as a raw material is known as a method for producing a perfluoroalkyne compound. A method for producing the perfluoroalkene compound used as the raw material involves reacting another perfluoroalkene compound with a perfluoroalkyl iodide in the presence of a catalyst (Non-Patent Document 1). Another known catalyst is one produced by fluorinating aluminum chloride (Non-Patent Document 1). Fluorinating agents used in fluorination include chlorofluorocarbons (hereinafter also referred to as "CFCs," e.g., trichlorofluoromethane (CClF)) and hydrochlorofluorocarbons (hereinafter also referred to as "HCFCs," e.g., chlorodifluoromethane (CHClF)) (Patent Document 1, Non-Patent Document 1). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] U.S. Patent No. 5,157,171 [Non-patent literature]

[0004] [Non-Patent Document 1] Journal of Fluorine Chemistry,102(2000),199-204 Summary of the Invention [Problem to be solved by the invention]

[0005] In a method for producing perfluoroalkene compounds, the reaction of other perfluoroalkene compounds with perfluoroalkyl iodides using fluorinated aluminum chloride obtained by fluorination with CFCs as a catalyst can produce perfluoroalkene compounds in relatively high yields. However, trichlorofluoromethane (CCl3F), a common CFC, is difficult to obtain.

[0006] On the other hand, in a method for producing a perfluoroalkene compound, when a perfluoroalkene compound is produced by reacting another perfluoroalkene compound with a perfluoroalkyl iodide using fluorinated aluminum chloride obtained by fluorination with HCFC as a catalyst, it has been revealed through investigation that there is room for improving the yield.

[0007] The present disclosure has been made in view of the above circumstances, and aims to provide a method for producing a perfluoroalkene compound that enables the production of a perfluoroalkene compound in high yield. Another aim of the present disclosure is to provide a composition having a high content of the perfluoroalkene compound. [Means for solving the problem]

[0008] The present disclosure encompasses the following configurations.

[0009] Item 1. A method for producing a first perfluoroalkene compound, a step of reacting a second perfluoroalkene compound with a perfluoroalkyl iodide in the presence of a fluorinated aluminum chloride-containing catalyst to obtain the first perfluoroalkene compound; The fluorinated aluminum chloride-containing catalyst is obtained by removing at least a portion of by-products from a product obtained by reacting aluminum chloride in the presence of a hydrochlorofluorocarbon; The first perfluoroalkene compound is represented by Formula 1: The second perfluoroalkene compound is represented by formula 2: The perfluoroalkyl iodide is represented by formula 3. [ka] (In formula 1, R 1 ~R 5 each independently represents a fluorine atom or a perfluoroalkyl group. [ka] (In formula 2, R 3 ~R 5 is the same as above.) [ka] (In formula 3, R 1 and R 2 is the same as above.)

[0010] Item 2. The method for producing a first perfluoroalkene compound according to Item 1, wherein the reaction between the second perfluoroalkene compound and the perfluoroethyl iodide in the step is carried out in a liquid phase.

[0011] Item 3. The method for producing a first perfluoroalkene compound according to Item 1 or 2, wherein the hydrochlorofluorocarbon is one or both of trichlorofluoromethane and dichlorofluoromethane.

[0012] Item 4. The method for producing a first perfluoroalkene compound according to any one of Items 1 to 3, wherein at least a portion of the by-products is removed by drying the product.

[0013] Item 5. A composition comprising a perfluoroalkene compound, The perfluoroalkene compound is represented by formula 1: The content of the perfluoroalkene compound is 94 mol% or more, the composition further comprises CFCF=CClCF and CFHCl; the content of CFCF=CClCF is 0.0001 mol% or more and 3 mol% or less, The content of the C3F5HCl2 is 0.0001 mol% or more and 3 mol% or less. [ka] (In formula 1, R 1 ~R 5 each independently represents a fluorine atom or a perfluoroalkyl group.

[0014] Item 6. The content of CFCF=CClCF is 0.0001 mol% or more and 1.5 mol% or less, Item 6. The composition according to Item 5, wherein the content of C3F5HCl2 is 0.0001 mol% or more and 1.5 mol% or less. [Effects of the Invention]

[0015] According to the present disclosure, it is possible to provide a method for producing a perfluoroalkene compound that enables the production of a perfluoroalkene compound in high yield. Furthermore, according to the present disclosure, it is also possible to provide a composition having a high content of a perfluoroalkene compound. DETAILED DESCRIPTION OF THE INVENTION

[0016] Specific examples of a method for producing a perfluoroalkene compound and a composition according to one embodiment of the present disclosure (hereinafter also referred to as "the present embodiment") will be described below.

[0017] In this specification, the expression "A to B" means the upper and lower limits of a range (i.e., A or more and B or less), and when no unit is specified for A and a unit is specified only for B, the unit of A and the unit of B are the same.

[0018] In the present disclosure, when a compound or the like is represented by a chemical formula, unless the atomic ratio is particularly limited, it is intended to include any conventionally known atomic ratio, and should not necessarily be limited to only those within the stoichiometric range.

[0019] [Embodiment 1: Method for producing a perfluoroalkene compound] A method for producing a perfluoroalkene compound according to one embodiment of the present disclosure will be described. One embodiment of the present disclosure (hereinafter also referred to as "the present embodiment") is a method for producing a first perfluoroalkene compound, comprising: a step of reacting a second perfluoroalkene compound with a perfluoroalkyl iodide in the presence of a fluorinated aluminum chloride-containing catalyst to obtain the first perfluoroalkene compound; The fluorinated aluminum chloride-containing catalyst is obtained by removing at least a portion of by-products from a product obtained by reacting aluminum chloride in the presence of a hydrochlorofluorocarbon; The first perfluoroalkene compound is represented by Formula 1: The second perfluoroalkene compound is represented by formula 2: The perfluoroalkyl iodide is represented by formula 3. [ka] (In formula 1, R 1 ~R 5 each independently represents a fluorine atom or a perfluoroalkyl group. [ka] (In formula 2, R 3 ~R 5 is the same as above.) [ka] (In formula 3, R 1 and R 2 is the same as above.)

[0020] According to the present disclosure, it is possible to provide a method for producing a perfluoroalkene compound that enables the production of a perfluoroalkene compound in high yield. The reason for this is presumed to be as follows.

[0021] When a hydrochlorofluorocarbon is used as a fluorinating agent in the fluorination of aluminum chloride, in addition to fluorinated aluminum chloride, at least one by-product selected from the group consisting of CHF3, CHClF2, CHCl2F, and CHCl3 is likely to be produced. CHF3, CHClF2, CHCl2F, and CHCl3 are unstable and tend to react with at least one by-product selected from the group consisting of the second perfluoroalkene compound, perfluoroalkyl iodide, and the first perfluoroalkene compound. Therefore, such a reaction tends to produce compounds other than the perfluoroalkene compound (for example, an organic compound having 3 carbon atoms other than the perfluoroalkene compound). Therefore, in such a production method, the yield of the perfluoroalkene compound may be low.

[0022] In the first method for producing a perfluoroalkene compound according to this embodiment, the fluorinated aluminum chloride-containing catalyst is obtained by removing at least a portion of the by-products from the product obtained by reacting aluminum chloride in the presence of a hydrochlorofluorocarbon. As a result, the reaction of the by-products with the second perfluoroalkene compound and the like is suppressed, making it difficult to produce compounds other than the perfluoroalkene compound. As a result, the yield of the perfluoroalkene compound can be improved.

[0023] <Step of Obtaining First Perfluoroalkene Compound> The method for producing a first perfluoroalkene compound of the present disclosure comprises a step of reacting a second perfluoroalkene compound with a perfluoroalkyl iodide in the presence of a fluorinated aluminum chloride-containing catalyst to obtain the first perfluoroalkene compound (hereinafter also referred to simply as a "step of obtaining a first perfluoroalkene compound"). The phrase "comprising a 'step of obtaining a first perfluoroalkene compound'" means that the method may consist solely of the "step of obtaining a first perfluoroalkene compound," or may include other steps in addition to the "step of obtaining a first perfluoroalkene compound." Examples of the "other steps" include a "step of obtaining a fluorinated aluminum chloride-containing catalyst by removing at least a portion of by-products from a product obtained by reacting aluminum chloride in the presence of a hydrochlorofluorocarbon."

[0024] In the step of obtaining the first perfluoroalkene compound, the reaction between the second perfluoroalkene compound and perfluoroethyl iodide may be carried out in a liquid phase or a gas phase. The "reaction between the second perfluoroalkene compound and perfluoroethyl iodide" carried out in a liquid phase refers to subjecting a liquid second perfluoroalkene compound and liquid perfluoroethyl iodide to the reaction. The "reaction between the second perfluoroalkene compound and perfluoroethyl iodide" carried out in a gas phase refers to subjecting a gaseous second perfluoroalkene compound and gaseous perfluoroethyl iodide to the reaction. When carried out in a liquid phase, the reaction between the second perfluoroalkene compound and perfluoroethyl iodide may be carried out in a batch system or a flow system (continuous system), but is preferably carried out in a batch system. When the reaction is carried out in a gas phase, the reaction between the second perfluoroalkene compound and perfluoroethyl iodide may be carried out in a batch mode or a flow mode (continuous mode), but is preferably carried out in a flow mode.

[0025] In the step of obtaining the first perfluoroalkene compound, the reaction between the second perfluoroalkene compound and perfluoroethyl iodide is preferably carried out in a liquid phase. When carried out in a liquid phase compared to a gas phase, the yield of the perfluoroalkene compound tends to be lower, but according to the present disclosure, even when carried out in a liquid phase, it is possible to produce the perfluoroalkene compound in a high yield.

[0026] The reaction mechanism of the above "reaction between the second perfluoroalkene compound and perfluoroethyl iodide" is outlined below. [ka] In the above reaction mechanism, R 1 ~R 5 are as described below, "-IF" means a de-IF reaction, and "ACF" means a fluorinated aluminum chloride-containing catalyst.

[0027] In the above "reaction of a second perfluoroalkene compound with perfluoroethyl iodide," the ratio M2 / M1 of the amount of substance M2 of fluorinated aluminum chloride in the fluorinated aluminum chloride-containing catalyst to the amount of substance M1 of the second perfluoroalkene compound is preferably 0.001 or more and 3 or less. This makes it possible to further improve the yield of the perfluoroalkene compound. The ratio M2 / M1 is more preferably 0.005 or more and 2 or less, and even more preferably 0.01 or more and 1 or less.

[0028] In the above "reaction of the second perfluoroalkene compound with perfluoroethyl iodide", the ratio M3 / M1 of the amount of substance M3 of the perfluoroalkyl iodide to the amount of substance M1 of the second perfluoroalkene compound is preferably 0.1 or more and 1 or less. This makes it possible to further improve the yield of the perfluoroalkene compound. The ratio M3 / M1 is more preferably 0.1 or more and 0.6 or less, and even more preferably 0.1 or more and 0.2 or less.

[0029] When the reaction is carried out in a liquid phase, the temperature of the "reaction of the second perfluoroalkene compound with perfluoroethyl iodide" is preferably 25°C or higher and 80°C or lower. This can further improve the yield of the perfluoroalkene compound. The temperature is more preferably 30°C or higher and 75°C or lower, and even more preferably 35°C or higher and 70°C or lower.

[0030] When carried out in a gas phase, the temperature of the "reaction of the second perfluoroalkene compound with perfluoroethyl iodide" is preferably 10°C or higher and 80°C or lower. This can further improve the yield of the perfluoroalkene compound. The temperature is more preferably 20°C or higher and 75°C or lower, and even more preferably 25°C or higher and 70°C or lower.

[0031] When the reaction is carried out in a liquid phase, the pressure of the "reaction between the second perfluoroalkene compound and perfluoroethyl iodide" is preferably 10 kPaG or more and 2000 kPaG or less in gauge pressure. This can further improve the yield of the perfluoroalkene compound. The pressure is more preferably 20 kPaG or more and 1500 kPaG or less, and even more preferably 30 kPaG or more and 1000 kPaG or less in gauge pressure.

[0032] When the reaction is carried out in a gas phase, the pressure of the "reaction between the second perfluoroalkene compound and perfluoroethyl iodide" is preferably 10 kPaG or more and 2000 kPaG or less in gauge pressure. This can further improve the yield of the perfluoroalkene compound. The pressure is more preferably 20 kPaG or more and 1500 kPaG or less, and even more preferably 30 kPaG or more and 1000 kPaG or less in gauge pressure.

[0033] The time for the "reaction between the second perfluoroalkene compound and perfluoroethyl iodide" is preferably 0.1 seconds or more and 300 seconds or less. This can further improve the yield of the perfluoroalkene compound. The time is more preferably 0.5 seconds or more and 250 seconds or less, and even more preferably 1 second or more and 200 seconds or less.

[0034] In the "step of obtaining a first perfluoroalkene compound," a purification treatment may be carried out after the "reaction of a second perfluoroalkene compound with perfluoroethyl iodide" is completed. The method of the purification treatment is not particularly limited, and the purification treatment may be carried out by a conventionally known method.

[0035] <First perfluoroalkene compound> The first perfluoroalkene compound is represented by Formula 1. [ka] (In formula 1, R 1 ~R 5 each independently represents a fluorine atom or a perfluoroalkyl group. This makes it possible to further improve the yield of the perfluoroalkene compound.

[0036] In the above formula 1, the number of carbon atoms in the perfluoroalkyl group is preferably 1 or more and 3 or less. This can further improve the yield of the perfluoroalkene compound. In the above formula 1, the number of carbon atoms in the perfluoroalkyl group may be 1, 2, or 3.

[0037] Preferably, in the above formula 1, R 1 and R 3 ~R 5 In the above formula 1, at least one of R is a fluorine atom, more preferably at least two of R are fluorine atoms, even more preferably at least three of R are fluorine atoms, and most preferably all of R are fluorine atoms.2 is a perfluoroalkyl group. Preferably, in the above formula 1, R 1 and R 3 ~R 5 At least one of R is a fluorine atom, and 2 is a perfluoroalkyl group, and more preferably, R 1 and R 3 ~R 5 two or more of the above are fluorine atoms, and R 2 is a perfluoroalkyl group, and more preferably, R 1 and R 3 ~R 5 are fluorine atoms, and R 2 is a perfluoroalkyl group, and even more preferably, R 1 and R 3 ~R 5 are all fluorine atoms, and R 2 is a perfluoroalkyl group, and most preferably R 1 and R 3 ~R 5 are all fluorine atoms, and R 2 is a methyl group.

[0038] Examples of the first perfluoroene compound include CF2=CFCF3, CF2=CFCF2CF3, CF2=CFCF(CF3)2, CF2=CFC(CF3)3, CF3CF=CFCF3, CF3CF=CFCF2CF3, CF3CF=CFCF(CF3)2, CF3CF=CFC(CF3)3, (CF3)2C=CFCF3, (CF3)2C=CFCF2CF3, (CF3)2C=CFCF(CF3)2, (CF3)2C=CFC(CF3)3, and the like.

[0039] <Second perfluoroalkene compound> The second perfluoroalkene compound is represented by Formula 2. [ka] (In formula 2, R 3~R 5 is the same as above.) This makes it possible to further improve the yield of the perfluoroalkene compound.

[0040] In the above formula 2, the number of carbon atoms in the perfluoroalkyl group is preferably 1 or more and 3 or less. This can further improve the yield of the perfluoroalkene compound. In the above formula 2, the number of carbon atoms in the perfluoroalkyl group may be 1, 2, or 3.

[0041] Preferably, in the above formula 2, R 3 ~R 5 At least one of the above is a fluorine atom, more preferably at least two of the above are fluorine atoms, and even more preferably all of the above are fluorine atoms.

[0042] Examples of the second perfluoroalkene compound include CF2=CF2, CF2=CFCF3, CF2=C(CF3)2, CF3CF=CF2, CF3CF=CFCF3, CF3CF=C(CF3)2, C(CF3)2=CF2, C(CF3)2=CFCF3, C(CF3)2=C(CF3)2, etc. These second perfluoroalkene compounds can be used alone or in combination of two or more.

[0043] <Perfluoroalkyl iodide> Perfluoroalkyl iodides are represented by formula 3. [ka] (In formula 3, R 1 and R 2 is the same as above.) This makes it possible to further improve the yield of the perfluoroalkene compound.

[0044] In the above formula 3, the number of carbon atoms in the perfluoroalkyl group is preferably 1 or more and 3 or less. This makes it possible to further improve the yield of the perfluoroalkene compound. In the above formula 3, the number of carbon atoms in the perfluoroalkyl group may be 1, 2, or 3.

[0045] Preferably, in the above formula 3, R 1 is a fluorine atom. Preferably, in the above formula 3, R 2 is a perfluoroalkyl group. Preferably, in the above formula 3, R 1 is a fluorine atom, and R 2 is a perfluoroalkyl group, and more preferably, R 1 is a fluorine atom, and R 2 is a methyl group.

[0046] Examples of perfluoroalkyl iodides represented by formula 3 include CF3CF2I, (CF3)2CFI, CF3I, etc. These perfluoroalkyl iodides represented by formula 3 can be used alone or in combination of two or more.

[0047] <Fluorinated aluminum chloride-containing catalyst> The fluorinated aluminum chloride-containing catalyst is obtained by removing at least a portion of the by-products from the product obtained by reacting aluminum chloride in the presence of a hydrochlorofluorocarbon, which is a fluorinating agent. This allows the content of by-products in the fluorinated aluminum chloride-containing catalyst to be kept low, thereby improving the yield of the perfluoroalkene compound. In the present disclosure, the "product obtained by reacting aluminum chloride in the presence of a hydrochlorofluorocarbon" may include the hydrochlorofluorocarbon and / or aluminum chloride that were not used in the reaction. In the present disclosure, the "by-product" refers to components other than the fluorinated aluminum chloride in the "product obtained by reacting aluminum chloride in the presence of a hydrochlorofluorocarbon."

[0048] The hydrochlorofluorocarbon is preferably one or both of trichlorofluoromethane and dichlorofluoromethane, which can further improve the yield of the perfluoroalkene compound.

[0049] The product includes a fluorinated aluminum chloride-containing catalyst and by-products. The product may consist of the fluorinated aluminum chloride-containing catalyst and by-products, or may further include other components (e.g., the hydrochlorofluorocarbon and / or the aluminum chloride) in addition to the fluorinated aluminum chloride-containing catalyst and by-products.

[0050] The by-product may be, for example, at least one selected from the group consisting of CHF3, CHClF2, CHCl2F, and CHCl3.

[0051] The content of fluorinated aluminum chloride in the fluorinated aluminum chloride-containing catalyst is preferably 0.01% by mass or more and 100% by mass or less. This can further improve the yield of the perfluoroalkene compound. The content is more preferably 0.1% by mass or more and 100% by mass or less, and even more preferably 1% by mass or more and 100% by mass or less.

[0052] The content of fluorinated aluminum chloride in the fluorinated aluminum chloride-containing catalyst can be determined by energy dispersive X-ray fluorescence analysis (EDX).

[0053] The amount of the fluorinated aluminum chloride-containing catalyst used can be a catalytic amount and is not particularly limited, but from the viewpoints of achieving a particularly high reaction conversion rate, easily reducing deterioration of the fluorinated aluminum chloride-containing catalyst, and easily suppressing deterioration of the fluorinated aluminum chloride-containing catalyst even when the isomerization reaction is carried out over a long period of time, for example, the weight ratio of the catalyst to the hourly supply rate of the second perfluoroalkene compound (W / F) is preferably 0.1 to 200 g sec / cc, more preferably 0.5 to 150 g sec / cc. The above "W / F" specifies the catalyst amount particularly for a gas-phase reaction, but even when a liquid-phase reaction is adopted, the amount of the catalyst used can be a catalytic amount and can be adjusted appropriately.

[0054] The fluorinated aluminum chloride-containing catalyst may be produced by carrying out the above-mentioned other step (i.e., a step other than the "step of obtaining a first perfluoroalkene compound"), namely, the "step of obtaining a fluorinated aluminum chloride-containing catalyst by removing at least a portion of the by-products from a product obtained by reacting aluminum chloride in the presence of a hydrochlorofluorocarbon as a fluorinating agent." The "step of obtaining a fluorinated aluminum chloride-containing catalyst by removing at least a portion of the by-products from a product obtained by reacting aluminum chloride in the presence of a hydrochlorofluorocarbon as a fluorinating agent" can include the "step of obtaining a product by reacting aluminum chloride in the presence of a hydrochlorofluorocarbon" (hereinafter also simply referred to as the "step of obtaining a product") and the "step of obtaining a fluorinated aluminum chloride-containing catalyst by removing at least a portion of the by-products from the above product" (hereinafter also simply referred to as the "step of obtaining a fluorinated aluminum chloride-containing catalyst").

[0055] <Steps for obtaining the product> In the step of obtaining the above-mentioned product, the reaction of aluminum chloride in the presence of hydrochlorofluorocarbon (hereinafter also simply referred to as "aluminum chloride reaction") may be carried out in a liquid phase or a gas phase. When carried out in a liquid phase, the aluminum chloride reaction may be carried out in a batch mode or a flow mode (continuous mode), with the batch mode being preferred. When carried out in a gas phase, the aluminum chloride reaction may be carried out in a batch mode or a flow mode (continuous mode), with the flow mode being preferred.

[0056] In the above "reaction of aluminum chloride," the ratio m2 / m1 of the amount of substance m2 of hydrochlorofluorocarbon to the amount of substance m1 of aluminum chloride is preferably 0.01 or more and 10 or less. This makes it easier to produce fluorinated aluminum chloride, thereby further improving the yield of the perfluoroalkene compound. The ratio m2 / m1 is more preferably 0.1 or more and 5 or less.

[0057] When the reaction is carried out in a liquid phase, the temperature of the "aluminum chloride reaction" is preferably -50°C or higher and 100°C or lower. This makes it easier to produce fluorinated aluminum chloride, thereby further improving the yield of the perfluoroalkene compound. The temperature is more preferably -40°C or higher and 90°C or lower, and even more preferably -20°C or higher and 80°C or lower.

[0058] When carried out in a gas phase, the temperature of the "aluminum chloride reaction" is preferably 0°C or higher and 600°C or lower. This makes it easier to produce fluorinated aluminum chloride, thereby further improving the yield of the perfluoroalkene compound. The temperature is more preferably 10°C or higher and 500°C or lower, and even more preferably 20°C or higher and 400°C or lower.

[0059] When carried out in a liquid phase, the pressure of the "aluminum chloride reaction" is preferably -50 kPaG or more and 2000 kPaG or less in gauge pressure. This makes it easier to produce fluorinated aluminum chloride, thereby further improving the yield of the perfluoroalkene compound. The pressure is more preferably -40 kPaG or more and 1700 kPaG or less in gauge pressure, and even more preferably 0 kPaG or more and 1500 kPaG or less. The lower limit of the pressure may be -50 kPaG, 0 kPaG, 50 kPaG, 100 kPaG, 150 kPaG, or 200 kPaG.

[0060] When carried out in a gas phase, the pressure of the "aluminum chloride reaction" is preferably 0 kPaG or more and 2000 kPaG or less in gauge pressure. This makes it easier to produce fluorinated aluminum chloride, thereby further improving the yield of the perfluoroalkene compound. The pressure is more preferably 5 kPaG or more and 1800 kPaG or less in gauge pressure, and even more preferably 10 kPaG or more and 1000 kPaG or less. The lower limit of the pressure may be 0 kPaG, 50 kPaG, 100 kPaG, 150 kPaG, or 200 kPaG.

[0061] The time for the "aluminum chloride reaction" (in other words, the contact time between aluminum chloride and the hydrochlorofluorocarbon fluorinating agent) is preferably 0.1 seconds or more and 120 seconds or less. This makes it easier to produce fluorinated aluminum chloride, thereby further improving the yield of the perfluoroalkene compound. The time is more preferably 1 second or more and 75 seconds or less.

[0062] <Step of obtaining a fluorinated aluminum chloride-containing catalyst> The removal of at least a portion of the by-products is preferably carried out at a temperature of 0° C. or higher and 200° C. or lower. This facilitates sufficient removal of the by-products, thereby further improving the yield of the perfluoroalkene compound. The removal of at least a portion of the by-products is more preferably carried out at a temperature of 5° C. or higher and 150° C. or lower.

[0063] The removal of at least a portion of the by-products is preferably carried out at a gauge pressure of -100 kPaG or more and 100 kPaG or less. This facilitates sufficient removal of the by-products, thereby further improving the yield of the perfluoroalkene compound. The removal of at least a portion of the by-products is more preferably carried out at a gauge pressure of 0.1 kPaG or more and 80 kPaG or less.

[0064] The removal of at least a portion of the by-products is preferably carried out for 1 second to 2 days. This facilitates sufficient removal of the by-products, thereby further improving the yield of the perfluoroalkene compound. The removal of at least a portion of the by-products is more preferably carried out for 1 minute to 1 day.

[0065] It is preferable to remove at least a portion of the by-products by drying the product. This can further improve the yield of the perfluoroalkene compound. The method for drying the product is not particularly limited, and the product may be dried, for example, under reduced pressure.

[0066] The effects of the present disclosure can be obtained by removing at least a portion of the by-products from the product, but to obtain a more significant effect, it is preferable that a larger amount of the by-products be removed.

[0067] <Application> The first perfluoroalkene compound obtained by the method for producing a perfluoroalkene compound of the present embodiment can be effectively used, for example, as an etching gas, etc. Etching gases are useful for forming cutting-edge microstructures in semiconductors, liquid crystals, etc.

[0068] [Embodiment 2: Composition] The composition according to this embodiment will be described. The present embodiment provides a composition comprising a perfluoroalkene compound, The perfluoroalkene compound is represented by formula 1: The content of the perfluoroalkene compound is 94 mol% or more, the composition further comprises CFCF=CClCF and CFHCl; the content of CFCF=CClCF is 0.0001 mol% or more and 3 mol% or less, The content of C3F5HCl2 is 0.0001 mol % or more and 3 mol % or less. [ka] (In formula 1, R 1 ~R 5 each independently represents a fluorine atom or a perfluoroalkyl group.

[0069] According to the present disclosure, it is possible to provide a composition having a high content of perfluoroalkene compounds.

[0070] ≪Composition≫ The composition of the present disclosure contains a perfluoroalkene compound, which will be described later. The composition of the present disclosure further contains CFCF=CClCF and CFHCl, which will be described later. The composition of the present disclosure may consist of the perfluoroalkene compound, CFCF=CClCF, and CFHCl, or may contain other components in addition to the perfluoroalkene compound, CFCF=CClCF, and CFHCl. Examples of other components include "organic compounds having three carbon atoms other than the first perfluoroalkene compound" excluding CFHCl. Examples of "organic compounds having three carbon atoms other than the first perfluoroalkene compound" include, in addition to CFHCl, at least one organic compound selected from the group consisting of CFHCl, CFHCl, and CFHCl.

[0071] <Perfluoroalkene compounds> The content of the perfluoroalkene compound is 94 mol% or more. As a result, the composition of the present disclosure contains the perfluoroalkene compound at a high concentration of 94 mol% or more, making it possible to provide a composition with a high content of the perfluoroalkene compound. The lower limit of the content of the perfluoroalkene compound is preferably 94.7 mol% or more, 95 mol% or more, 95.8 mol% or more, 96 mol% or more, 96.6 mol% or more, 97 mol% or more, 98 mol% or more, or 99 mol% or more. The upper limit of the content of the perfluoroalkene compound is preferably 100 mol% or less.

[0072] The content of perfluoroalkene compounds can be determined by combining mass analysis by gas chromatography / mass spectrometry (GC / MS) performed using a gas chromatography (trade name "GC-2014") manufactured by Shimadzu Corporation with structural analysis by NMR spectroscopy performed using an NMR (trade name "400YH") manufactured by JEOL.

[0073] The perfluoroalkene compound according to this embodiment is similar to the first perfluoroalkene compound according to the first embodiment, and therefore, a description thereof will be omitted here.

[0074] <CF3CF=CClCF3> The content of CF3CF=CClCF3 is 0.0001 mol% or more and 3 mol% or less. The lower limit of the content of CF3CF=CClCF3 may be 0.001 mol% or more, 0.01 mol% or more, 0.1 mol% or more, 1.0 mol% or more, or 1.2 mol% or more. From the viewpoint of storage stability of the product (more specifically, the perfluoroalkene compound), the upper limit of the content of CF3CF=CClCF3 is preferably 2.9 mol% or less, 2.8 mol% or less, 2.7 mol% or less, 2.6 mol% or less, 2.5 mol% or less, 2.4 mol% or less, 2.3 mol% or less, or 2.2 mol% or less. From the viewpoint of suppressing decomposition of the product (more specifically, the perfluoroalkene compound), the content of CF3CF=CClCF3 is preferably 0.0001 mol% or more and 1.5 mol% or less.

[0075] The content of CF3CF=CClCF3 can be determined by combining mass analysis by gas chromatography / mass spectrometry (GC / MS) performed using a gas chromatography (trade name "GC-2014") manufactured by Shimadzu Corporation, and structural analysis by NMR spectroscopy performed using an NMR (trade name "400YH") manufactured by JEOL.

[0076] <c3f5hcl2> The content of C3F5HCl2 is 0.0001 mol% or more and 3 mol% or less. The lower limit of the content of C3F5HCl2 may be 0.001 mol% or more, 0.01 mol% or more, 0.1 mol% or more, or 0.5 mol% or more. From the viewpoint of storage stability of the product (more specifically, the perfluoroalkene compound), the upper limit of the content of C3F5HCl2 is preferably 2 mol% or less, more preferably 1.5 mol% or less, and even more preferably 1.3 mol% or less. From the viewpoint of suppressing decomposition of the product (more specifically, the perfluoroalkene compound), the content of C3F5HCl2 is preferably 0.0001 mol% or more and 1.5 mol% or less.

[0077] The C3F5HCl2 content can be determined by combining mass analysis by gas chromatography / mass spectrometry (GC / MS) performed using a gas chromatography (trade name "GC-2014") manufactured by Shimadzu Corporation, and structural analysis by NMR spectroscopy performed using an NMR (trade name "400YH") manufactured by JEOL.

[0078] <Application> The composition of the present embodiment can be effectively used, for example, as a raw material for producing a perfluoroalkyne compound, which is useful, for example, as an etching gas.

[0079] <<Method for producing composition>> The composition of this embodiment can be produced, for example, by the method for producing a perfluoroalkene compound described in embodiment 1.

[0080] Although the embodiments of the present disclosure have been described above, various changes in form and details are possible without departing from the spirit and scope of the claims. [Example]

[0081] The present embodiment will be described in more detail with reference to examples, although the present embodiment is not limited to these examples.

[0082] <Preparation of the first perfluoroalkene compound> <Preparation of Fluorinated Aluminum Chloride-Containing Catalyst> The first perfluoroalkene compounds of Samples 1 to 3 and Sample 11 were prepared as follows.

[0083] First, aluminum chloride was added in the amount shown in Table 1 to a metal reaction vessel, and the vessel was sealed with a lid. The fluorinating agent shown in Table 1 was then added in the amount shown in Table 1. In Table 1, R22 refers to chlorodifluoromethane (CHClF2). Next, the aluminum chloride and the fluorinating agent were stirred at 25°C (room temperature) and under the pressure shown in Table 1, allowing the aluminum chloride fluorination reaction to proceed. Sampling was performed as needed to determine the end of the fluorination reaction when no change in the composition of the reaction system was observed. Next, in cases where "Yes" is listed in the "Whether or Not Distillation Under Reduced Pressure" column of Table 1, components other than fluorinated aluminum chloride were distilled off by reducing the pressure in the metal reaction vessel to -100 kPaG (i.e., by drying). In the "Whether or Not Distillation Under Reduced Pressure" column of Table 1, "No" means that distillation under reduced pressure of components other than fluorinated aluminum chloride was not performed. Thus, a fluorinated aluminum chloride-containing catalyst for each sample was prepared.

[0084] <Preparation of First Perfluoroalkene Compound> Next, into the metal reaction vessel from which components other than fluorinated aluminum chloride had been distilled off, the amount of tetrafluoroethylene (CF2=CF2) (i.e., the second perfluoroalkene compound) and the amount of pentafluoroiodide (CF3CF2I) (i.e., the perfluoroalkyl iodide) listed in Table 2 were charged, and the mixture was stirred under the temperature and pressure conditions listed in Table 1 to allow the "reaction between the second perfluoroalkene compound and perfluoroethyl iodide" to proceed. Sampling was carried out as needed, and the reaction was completed when no further change in the composition of the reaction system was observed. The composition was determined by mass analysis by gas chromatography / mass spectrometry (GC / MS) using a Shimadzu gas chromatograph (product name "GC-2014") and structural analysis by NMR spectroscopy using a JEOL NMR (product name "400YH").

[0085] As a result, perfluoroalkene compounds Samples 1 to 3 and Sample 11 were obtained in the form of compositions containing the first perfluoroalkene compound. Mass analysis of the compositions was performed by gas chromatography / mass spectrometry (GC / MS) using a Shimadzu Gas Chromatography (product name "GC-2014"), and structural analysis by NMR spectroscopy was performed using a JEOL NMR (product name "400YH"), confirming that the first perfluoroalkene compound (specifically, CF3-CF=CF-CF3) was produced, and that the conversion rate was as shown in Table 2. Here, the conversion rate refers to the ratio [%] of the total amount [mol] of compounds other than the raw material compound contained in the gas effluent from the metal reaction vessel to the amount [mol] of the raw material compound supplied to the metal reaction vessel.

[0086] <Content of First Perfluoroalkene Compound> For the composition related to each sample, using the method described in Embodiment 2, it was measured that the first perfluoroalkene compound contained in the composition is "CF3-CF=CF-CF3" and the content of "CF3-CF=CF-CF3". The obtained results are recorded in the column of "First perfluoroalkene compound" in Table 3. That the content of the first perfluoroalkene compound is 94 mol% or more means that the perfluoroalkene compound could be obtained in a high yield.

[0087] <Content of CF3CF=CClCF3> For the composition related to each sample, using the method described in Embodiment 2, the content of CF3CF=CClCF3 was measured. The obtained results are recorded in the column of "CF3CF=CClCF3 [mol%]" in Table 3.

[0088] <Content of C3F5HCl2> For the composition related to each sample, using the method described in Embodiment 2, the content of C3F5HCl2 was measured. The obtained results are recorded in the column of "C3F5HCl2 [mol%]" in Table 3.

[0089]

Table 1

[0090]

Table 2

[0091]

Table 3

[0092] The methods for producing the first perfluoroalkene compound of Samples 1 to 3 correspond to Examples. The method for producing the first perfluoroalkene compound of Sample 11 corresponds to Comparative Example. It was confirmed that the methods for producing the first perfluoroalkene compound of Samples 1 to 3 exhibit an exceptionally excellent effect of enabling the production of a perfluoroalkene compound in high yield compared to the method for producing the first perfluoroalkene compound of Sample 11. Therefore, it was found that the methods for producing the first perfluoroalkene compound of Samples 1 to 3 enable the production of a perfluoroalkene compound in high yield.

Claims

1. A method for producing a first perfluoroalkene compound, comprising: a step of reacting a second perfluoroalkene compound with a perfluoroalkyl iodide in the presence of a fluorinated aluminum chloride-containing catalyst to obtain the first perfluoroalkene compound; The fluorinated aluminum chloride-containing catalyst is obtained by removing at least a portion of by-products from a product obtained by reacting aluminum chloride in the presence of a hydrochlorofluorocarbon; The first perfluoroalkene compound is represented by Formula 1: The second perfluoroalkene compound is represented by Formula 2: The first method for producing a perfluoroalkene compound, wherein the perfluoroalkyl iodide is represented by formula 3. 【Chemistry 1】 (In formula 1, R １ ~R ５ each independently represents a fluorine atom or a perfluoroalkyl group. 【Chemistry 2】 (In formula 2, R ３ ~R ５ is the same as above.) 【Transformation 3】 (In formula 3, R １ and R ２ is the same as above.)

2. 2. The method for producing a first perfluoroalkene compound according to claim 1, wherein in the step, the reaction between the second perfluoroalkene compound and the perfluoroethyl iodide is carried out in a liquid phase.

3. 3. The method for producing a first perfluoroalkene compound according to claim 1 or claim 2, wherein the hydrochlorofluorocarbon is one or both of trichlorofluoromethane and dichlorofluoromethane.

4. 3. The method for producing a first perfluoroalkene compound according to claim 1 or claim 2, wherein the removal of at least a portion of the by-products is carried out by drying the product.

5. A composition comprising a perfluoroalkene compound, The perfluoroalkene compound is represented by Formula 1: The content of the perfluoroalkene compound is 94 mol% or more, The composition is CF ３ CF=CClCF ３ and C ３ F ５ HCl ２ Further comprising: The CF ３ CF=CClCF ３ The content of is 0.0001 mol% or more and 3 mol% or less, Said C ３ F ５ HCl ２ The composition, wherein the content of is 0.0001 mol% or more and 3 mol% or less. 【Chemistry 4】 (In formula 1, R １ ~R ５ each independently represents a fluorine atom or a perfluoroalkyl group.

6. The CF ３ CF=CClCF ３ The content of is 0.0001 mol% or more and 1.5 mol% or less, Said C ３ F ５ HCl ２ The composition according to claim 5, wherein the content of is 0.0001 mol% or more and 1.5 mol% or less.

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