Perfluoroalkene compound production method and composition

Abstract

This method for producing a first perfluoroalkene compound involves a step for 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, wherein the fluorinated aluminum chloride-containing catalyst is obtained by reacting aluminum chloride in the presence of a hydrochlorofluorocarbon to obtain a product and removing at least part of a by-product therefrom; the first perfluoroalkene compound is represented by formula 1; the second perfluoroalkene compound is represented by formula 2; and the perfluoroalkyl iodide is represented by formula 3.

Description

Method for producing perfluoroalkene compounds and compositions

[0001] This disclosure relates to methods and compositions for producing perfluoroalkene compounds.

[0002] Perfluoroalkyne compounds have been conventionally used in semiconductor dry etching gases, various refrigerants, foaming agents, and heat transfer media. Furthermore, a method of producing perfluoroalkyne compounds using perfluoroalkene compounds as raw materials is known. A method of 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 Literature 1). A catalyst produced by fluorinating aluminum chloride is also known (Non-Patent Literature 1). Fluorinating agents used in this process include chlorofluorocarbons (hereinafter also referred to as "CFCs"). For example, trichlorofluoromethane (CCl) ３ F)) and hydrochlorofluorocarbons (hereinafter also referred to as "HCFCs"). For example, chlorodifluoromethane (HClF) ２ Examples include (Patent Document 1, Non-Patent Document 1).

[0003] U.S. Patent No. 5157171

[0004] Journal of Fluorine Chemistry, 102 (2000), 199-204

[0005] In a method for producing perfluoroalkene compounds, using fluorinated aluminum chloride obtained by fluorination with CFCs as a catalyst to react other perfluoroalkene compounds with perfluoroalkyl iodides allows for the production of perfluoroalkene compounds in relatively high yield. However, trichlorofluoromethane (CCl), which is a common CFC, is not suitable for this purpose. ３ F) is difficult to obtain.

[0006] On the other hand, in a method for producing a perfluoroalkene compound, when a reaction between another perfluoroalkene compound and a perfluoroalkyl iodide is carried out using aluminum fluoride chloride obtained by fluorination with HCFC as a catalyst to produce a perfluoroalkene compound, it has been revealed through studies that there is room for improving the yield.

[0007] The present disclosure has been made in view of the above circumstances, and an object thereof is to provide a method for producing a perfluoroalkene compound that enables the perfluoroalkene compound to be obtained in a high yield. Another object of the present disclosure is to provide a composition having a high content of the perfluoroalkene compound.

[0008] The present disclosure includes the following configurations.

[0009] Item 1. A method for producing a first perfluoroalkene compound, comprising a step of reacting a second perfluoroalkene compound and a perfluoroalkyl iodide in the presence of an aluminum fluoride chloride-containing catalyst to obtain the first perfluoroalkene compound, wherein the aluminum fluoride chloride-containing catalyst is obtained by removing at least a part 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, and the perfluoroalkyl iodide is represented by Formula 3. A method for producing a first perfluoroalkene compound. (In Formula 1, R １ ~R ５ each independently represents a fluorine atom or a perfluoroalkyl group.) (In Formula 2, R ３ ~R ５ are the same as defined above.) (In Formula 3, R １ and R ２ are the same as defined above.)

[0010] [Correction based on Rule 91 14.05.2026] Item 2. A method for producing the first perfluoroalkene compound according to Item 1, wherein the reaction between the second perfluoroalkene compound and the perfluoroalkyl iodide is carried out in the liquid phase.

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

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

[0013] Item 5. A composition comprising a perfluoroalkene compound, wherein the perfluoroalkene compound is represented by formula 1, the content of the perfluoroalkene compound is 94 mol% or more, and the composition is CF ３ CF = CClCF ３ and C ３ F ５ HCl ２ The CF further includes ３ CF = CClCF ３ The content of is 0.0001 mol% or more and 3 mol% or less, and the above C ３ F ５ HCl ２ A composition having a content of 0.0001 mol% or more and 3 mol% or less. (In formula 1, R １ ~R ５ Each of these independently represents either a fluorine atom or a perfluoroalkyl group.

[0014] Item 6. Said CF ３ CF = CClCF ３ The content of is 0.0001 mol% or more and 1.5 mol% or less, and the above C ３ F ５ HCl ２ The composition according to item 5, wherein the content of is 0.0001 mol% or more and 1.5 mol% or less.

[0015] This disclosure provides a method for producing perfluoroalkene compounds that enables the acquisition of perfluoroalkene compounds in high yield. Furthermore, this disclosure also provides a composition with a high content of perfluoroalkene compounds.

[0016] A specific example of a method for producing a perfluoroalkene compound and a composition according to one embodiment of the present disclosure (hereinafter also referred to as "this embodiment") is described below.

[0017] In this specification, the notation "A to B" means an upper and lower limit of a range (i.e., A or greater and B or less), and if no unit is specified for A, but a unit is specified only for B, the unit for A and the unit for B are the same.

[0018] In this disclosure, when compounds and the like are represented by chemical formulas, unless otherwise specified, the atomic ratios should include all conventionally known atomic ratios and should not necessarily be limited to those within the stoichiometric range.

[0019] [Embodiment 1: Method for Producing Perfluoroalkene Compounds] A method for producing perfluoroalkene compounds according to one embodiment of the present disclosure will be described. One embodiment of the present disclosure (hereinafter also referred to as "this embodiment") is a method for producing a first perfluoroalkene compound, comprising the step of reacting a second perfluoroalkene compound and a perfluoroalkyl iodide in the presence of a fluorinated aluminum chloride-containing catalyst to obtain the first perfluoroalkene compound, wherein the fluorinated aluminum chloride-containing catalyst is obtained by removing at least a portion of the 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, and the perfluoroalkyl iodide is represented by formula 3. (In formula 1, R １ ~R ５ Each of these independently represents either a fluorine atom or a perfluoroalkyl group. (In formula 2, R ３ ~R ５ (This is the same as above.) (In formula 3, R １ and R ２ (This is the same as above.)

[0020] This disclosure provides a method for producing perfluoroalkene compounds that enables the acquisition of perfluoroalkene compounds in high yield. The reason for this is presumed to be as follows.

[0021] In the fluorination of aluminum chloride, when hydrochlorofluorocarbon is used as the fluorinating agent, CHF is produced as a byproduct in addition to fluorinated aluminum chloride. ３ , CHClF ２ , CHCl ２ F, and CHCl ３ At least one species selected from the group consisting of CHF is more likely to occur. ３ , CHClF ２ , CHCl ２ F, and CHCl ３ Since the compound is unstable and readily reacts with at least one compound selected from the group consisting of a second perfluoroalkene compound, a perfluoroalkyl iodide, and a first perfluoroalkene compound, such reactions tend to produce compounds other than perfluoroalkene compounds (for example, organic compounds with three carbon atoms other than perfluoroalkene compounds). Therefore, the yield of the perfluoroalkene compound may be low in such production methods.

[0022] In the method for producing the first 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 between the by-products and the second perfluoroalkene compound is suppressed, making it difficult to produce compounds other than the perfluoroalkene compound. Consequently, the yield of the perfluoroalkene compound can be improved.

[0023] <Step to obtain the first perfluoroalkene compound> The method for producing the first perfluoroalkene compound according to the present disclosure comprises the 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 simply referred to as the "step to obtain the first perfluoroalkene compound"). The phrase "comprising the 'step to obtain the first perfluoroalkene compound'" means that the method may consist only of the "step to obtain the first perfluoroalkene compound," or it may include other steps in addition to the "step to obtain the first perfluoroalkene compound." Examples of "other steps" include the "step to obtain 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."

[0024] [Correction based on Rule 91 14.05.2026] In the step of obtaining the first perfluoroalkene compound described above, the reaction between the second perfluoroalkene compound and the perfluoroalkyl iodide may be carried out in the liquid phase or in the gas phase. The "reaction between the second perfluoroalkene compound and the perfluoroalkyl iodide" carried out in the liquid phase means that a liquid second perfluoroalkene compound and a liquid perfluoroalkyl iodide are subjected to the reaction. The "reaction between the second perfluoroalkene compound and the perfluoroalkyl iodide" carried out in the gas phase means that a gaseous second perfluoroalkene compound and a gaseous perfluoroalkyl iodide are subjected to the reaction. When carried out in the liquid phase, the reaction between the second perfluoroalkene compound and the perfluoroalkyl iodide may be in batch mode or flow mode (continuous mode), but is preferably in batch mode. When carried out in the gas phase, the reaction between the second perfluoroalkene compound and the perfluoroalkyl iodide may be in batch mode or flow mode (continuous mode), but flow mode is preferred.

[0025] [Correction based on Rule 91 14.05.2026] In the step of obtaining the first perfluoroalkene compound described above, the reaction between the second perfluoroalkene compound and the perfluoroalkyl iodide is preferably carried out in the liquid phase. When carried out in the liquid phase compared to the gas phase, the yield of the perfluoroalkene compound tends to decrease, but according to this disclosure, it is possible to produce the perfluoroalkene compound in high yield even when carried out in the liquid phase.

[0026] [Correction based on Rule 91, 14.05.2026] The reaction mechanism of the above "reaction between the second perfluoroalkene compound and perfluoroalkyl iodide" is outlined below. Furthermore, in the above reaction mechanism, R １ ~R ５ As will be explained later, "-IF" means the de-IF reaction, and "ACF" means a catalyst containing fluorinated aluminum chloride.

[0027] [Correction based on Rule 91 14.05.2026] In the above "reaction of a second perfluoroalkene compound with a perfluoroalkyl iodide", the ratio M2 / M1 of the amount of fluorinated aluminum chloride in the fluorinated aluminum chloride-containing catalyst to the amount of the second perfluoroalkene compound M1 is preferably 0.001 or more and 3 or less. This can 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] [Correction based on Rule 91 14.05.2026] In the above "reaction of a second perfluoroalkene compound with a perfluoroalkyl iodide", the ratio M3 / M1 of the amount of perfluoroalkyl iodide to the amount of the second perfluoroalkene compound M1 is preferably 0.1 or more and 1 or less. This can 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] [Correction based on Rule 91 14.05.2026] When carried out in liquid phase, the temperature of the "reaction of the second perfluoroalkene compound with the perfluoroalkyl iodide" is preferably 25°C to 80°C. This can further improve the yield of the perfluoroalkene compound. The temperature is more preferably 30°C to 75°C, and even more preferably 35°C to 70°C.

[0030] [Correction based on Rule 91 14.05.2026] When carried out in the gas phase, the temperature of the "reaction of the second perfluoroalkene compound with the perfluoroalkyl iodide" is preferably 10°C to 80°C. This can further improve the yield of the perfluoroalkene compound. The temperature is more preferably 20°C to 75°C, and even more preferably 25°C to 70°C.

[0031] [Correction based on Rule 91 14.05.2026] When carried out in liquid phase, the pressure of the "reaction of the second perfluoroalkene compound with the perfluoroalkyl iodide" is preferably 10 kPaG to 2000 kPaG in gauge pressure. This can further improve the yield of the perfluoroalkene compound. The pressure is more preferably 20 kPaG to 1500 kPaG in gauge pressure, and even more preferably 30 kPaG to 1000 kPaG in gauge pressure.

[0032] [Correction based on Rule 91 14.05.2026] When carried out in the gas phase, the pressure of the "reaction of the second perfluoroalkene compound with the perfluoroalkyl iodide" is preferably 10 kPaG to 2000 kPaG in gauge pressure. This can further improve the yield of the perfluoroalkene compound. The pressure is more preferably 20 kPaG to 1500 kPaG in gauge pressure, and even more preferably 30 kPaG to 1000 kPaG.

[0033] [Correction based on Rule 91 14.05.2026] The reaction time for the "second perfluoroalkene compound with perfluoroalkyl iodide" described above is preferably 0.1 seconds or more and 300 seconds or less. This can further improve the yield of the perfluoroalkene compound. The reaction 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] [Correction based on Rule 91 14.05.2026] In the "step for obtaining the first perfluoroalkene compound" described above, a purification process may be performed after the "reaction of the second perfluoroalkene compound with the perfluoroalkyl iodide" has been completed. The method of the purification process is not particularly limited, but the purification process may be carried out by conventionally known methods.

[0035] <First perfluoroalkene compound> The first perfluoroalkene compound is represented by formula 1. (In formula 1, R １ ~R ５ Each of these independently represents either a fluorine atom or a perfluoroalkyl group. This allows for a further improvement in the yield of perfluoroalkene compounds.

[0036] In Formula 1 above, 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 Formula 1 above, 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 One or more of the atoms are fluorine atoms, more preferably two or more are fluorine atoms, even more preferably three or more are fluorine atoms, and most preferably all are fluorine atoms. Also preferably, in the above formula 1, R ２ is a perfluoroalkyl group. Preferably, in the above formula 1, R １ and R ３ ~R ５One or more of them are fluorine atoms, and R ２ is a perfluoroalkyl group, more preferably, R １ and R ３ ~R ５ Two or more of them are fluorine atoms, and R ２ is a perfluoroalkyl group, even more preferably, R １ and R ３ ~R ５ Three or more of them are fluorine atoms, and R ２ is a perfluoroalkyl group, still more preferably, R １ and R ３ ~R ５ All of them are fluorine atoms, and R ２ is a perfluoroalkyl group, most preferably, R １ and R ３ ~R ５ All of them are fluorine atoms, and R ２ is a methyl group.

[0038] [Correction based on Rule 91, 14.05.2026] As the first perfluoroalkene compound, for example, CF ２ =CFCF ３ , CF ２ =CFCF ２ CF ３ , CF ２ =CFCF(CF ３ ) ２ , CF ２ =CFC(CF ３ ) ３ , CF ３ CF=CFCF ３ , CF ３ CF=CFCF ２ CF ３ , CF ３ CF=CFCF(CF ３ ) ２ , CF ３ CF=CFCCF ３ ) ３ , (CF ３ ) ２ C=CFCF ３ , (CF ３ ) ２C = CFCF ２ CF ３ 、(CF ３ ) ２ C = CFCF(CF ３ ) ２ 、(CF ３ ) ２ C = CFC(CF ３ ) ３ etc. can be cited.

[0039] <Second perfluoroalkene compound> The second perfluoroalkene compound is represented by Formula 2. (In Formula 2, R ３ ~R ５ are the same as above.) By this, the yield of the perfluoroalkene compound can be further improved.

[0040] In the above Formula 2, the number of carbon atoms of the perfluoroalkyl group is preferably 1 or more and 3 or less. By this, the yield of the perfluoroalkene compound can be further improved. In the above Formula 2, the number of carbon atoms of the perfluoroalkyl group may be 1, may be 2, or may be 3.

[0041] Preferably, in the above Formula 2, any one or more of R ３ ~R ５ are fluorine atoms, more preferably any two or more are fluorine atoms, and even more preferably all are fluorine atoms.

[0042] Examples of the second perfluoroalkene compound include, for example, CF ２ = CF ２ , CF ２ = CFCF ３ , CF ２ = C(CF ３ ) ２ , CF ３ CF = CF ２ , CF ３ CF = CFCF ３ , CF ３ CF = C(CF ３ ) ２ , C(CF ３ ) ２ = CF ２ , C(CF ３ ) ２= CFCF ３ , C (CF ３ ) ２ = C(CF ３ ) ２ These are some examples. These second perfluoroalkene compounds can be used individually or in combination of two or more.

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

[0044] In Formula 3 above, 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 Formula 3 above, 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, more preferably R １ is a fluorine atom, and R ２ It is a methyl group.

[0046] Examples of perfluoroalkyl iodides represented by formula 3 include CF ３ CF ２ I, (CF ３ ) ２ CFI, CF ３ Examples include I. These perfluoroalkyl iodides represented by formula 3 can be used individually or in combination of two or more types.

[0047] <Fluorinated Aluminum Chloride-Containing Catalyst> A 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 fluorinating agent, hydrochlorofluorocarbon. This allows for a reduction in the by-product content in the fluorinated aluminum chloride-containing catalyst, thereby improving the yield of the perfluoroalkene compound. In this disclosure, "the product obtained by reacting aluminum chloride in the presence of hydrochlorofluorocarbon" may include hydrochlorofluorocarbon and / or aluminum chloride that were not used in the reaction. In this disclosure, "by-product" refers to components other than fluorinated aluminum chloride in "the product obtained by reacting aluminum chloride in the presence of hydrochlorofluorocarbon".

[0048] The above-mentioned hydrochlorofluorocarbon is preferably one or both of trichlorofluoromethane and dichlorofluoromethane. This can further improve the yield of the perfluoroalkene compound.

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

[0050] Examples of by-products include CHF ３ , CHClF ２ , CHCl ２ F, and CHCl ３ At least one selected from the group consisting of the following is mentioned.

[0051] The content of aluminum fluoride in the aluminum fluoride 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 a catalyst containing fluorinated aluminum chloride can be determined by energy-dispersive X-ray fluorescence analysis (EDX).

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

[0054] The fluorinated aluminum chloride-containing catalyst may also be produced by performing the "step of obtaining a fluorinated aluminum chloride-containing catalyst 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" as one of the other steps described above (i.e., a step other than the "step of obtaining a first perfluoroalkene compound"). The "step of obtaining a fluorinated aluminum chloride-containing catalyst 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" may 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 the 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] <Step to obtain the product> In the step to obtain the above product, the reaction of aluminum chloride in the presence of hydrochlorofluorocarbon (hereinafter also simply referred to as "reaction of aluminum chloride") may be carried out in the liquid phase or in the gas phase. When carried out in the liquid phase, the reaction of aluminum chloride may be in batch mode or flow mode (continuous mode), but it is preferably in batch mode. When carried out in the gas phase, the reaction of aluminum chloride may be in batch mode or flow mode (continuous mode), but it is preferably in flow mode.

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

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

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

[0059] When carried out in liquid phase, the pressure of the "aluminum chloride reaction" described above is preferably -50 kPaG to 2000 kPaG in gauge pressure. This makes it easier to produce fluorinated aluminum chloride, thereby improving the yield of the perfluoroalkene compound. The pressure is more preferably -40 kPaG to 1700 kPaG in gauge pressure, and even more preferably 0 kPaG to 1500 kPaG. 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 the gas phase, the pressure of the "aluminum chloride reaction" described above is preferably 0 kPaG to 2000 kPaG in gauge pressure. This makes it easier to produce fluorinated aluminum chloride, thereby improving the yield of the perfluoroalkene compound. The pressure is more preferably 5 kPaG to 1800 kPaG in gauge pressure, and even more preferably 10 kPaG to 1000 kPaG. 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" described above (in other words, the contact time between aluminum chloride and the hydrochlorofluorocarbon, which is a fluorinating agent) is preferably 0.1 seconds or more and 120 seconds or less. This makes it easier to produce fluorinated aluminum chloride, thereby improving the yield of the perfluoroalkene compound. More preferably, this time is 1 second or more and 75 seconds or less.

[0062] <Step to obtain a catalyst containing fluorinated aluminum chloride> It is preferable to remove at least a portion of the by-products at a temperature of 0°C to 200°C. This makes it easier to remove the by-products sufficiently, thereby improving the yield of the perfluoroalkene compound. It is even more preferable to remove at least a portion of the by-products at a temperature of 5°C to 150°C.

[0063] The removal of at least a portion of the by-products is preferably carried out at a gauge pressure of -100 kPaG to 100 kPaG. This makes it easier to remove the by-products sufficiently, thereby 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 to 80 kPaG.

[0064] It is preferable that the removal of at least some of the by-products be carried out within 1 second to 2 days. This makes it easier to remove the by-products sufficiently, thereby further improving the yield of the perfluoroalkene compound. It is even more preferable that the removal of at least some of the by-products be carried out within 1 minute to 1 day.

[0065] At least a portion of the by-products is preferably removed by drying the product. This can further improve the yield of the perfluoroalkene compound. The method of drying the product is not particularly limited, but drying may be carried out, for example, by "reduced pressure".

[0066] The effects of this 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 by-products are removed.

[0067] <Applications> The first perfluoroalkene compound obtained by the method for producing the perfluoroalkene compound of this embodiment can be effectively used in applications such as etching gases. Etching gases are useful for forming cutting-edge microstructures in semiconductors, liquid crystals, and the like.

[0068] [Embodiment 2: Composition] The composition according to this embodiment will be described. This embodiment is a composition comprising a perfluoroalkene compound, wherein the perfluoroalkene compound is represented by formula 1, the content of the perfluoroalkene compound is 94 mol% or more, and the composition is CF ３ CF = CClCF ３ and C ３ F ５ HCl ２ The CF further includes ３ CF = CClCF ３ The content of is 0.0001 mol% or more and 3 mol% or less, and C ３ F ５ HCl ２ The content is between 0.0001 mol% and 3 mol%. (In formula 1, R １ ~R ５ Each of these independently represents either a fluorine atom or a perfluoroalkyl group.

[0069] According to this disclosure, it is possible to provide a composition with a high content of perfluoroalkene compounds.

[0070] ≪Composition≫ The composition of this disclosure contains a perfluoroalkene compound as described below. The composition of this disclosure contains a perfluoroalkene compound as described below. ３ CF = CClCF ３ and C, which will be discussed later. ３ F ５ HCl ２ The compositions of this disclosure include perfluoroalkene compounds, CF ３ CF = CClCF３ , and C ３ F ５ HCl ２ It may also be a perfluoroalkene compound, CF ３ CF = CClCF ３ , and C ３ F ５ HCl ２ In addition, other components may be included. Other components include, for example, C ３ F ５ HCl ２ Examples of "organic compounds with 3 carbon atoms other than the first perfluoroalkene compound" are listed below. ３ F ５ HCl ２ In addition, for example, C ３ F ４ HCl ３ , C ３ F ５ H ２ Cl ２ , and C ３ F ５ H ３ This includes at least one organic compound selected from the group consisting of Cl.

[0071] <Perfluoroalkene Compounds> The perfluoroalkene compound content is 94 mol% or more. As a result, the composition of this disclosure contains perfluoroalkene compounds at a high concentration of 94 mol% or more, making it possible to provide a composition with a high perfluoroalkene compound content. The lower limit of the perfluoroalkene compound content 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 perfluoroalkene compound content is preferably 100 mol% or less.

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

[0073] Since the perfluoroalkene compound according to this embodiment is the same as the first perfluoroalkene compound according to Embodiment 1, its description will be omitted here.

[0074] <CF ３ CF = CClCF ３ > CF ３ CF = CClCF ３ The content is between 0.0001 mol% and 3 mol%. CF ３ CF = CClCF ３ The lower limit of the content 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 the storage stability of the product (more specifically, the perfluoroalkene compound), CF ３ CF = CClCF ３ The upper limit of the content 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 the decomposition of the product (more specifically, the perfluoroalkene compound), CF ３ CF = CClCF ３ The content of is preferably 0.0001 mol% or more and 1.5 mol% or less.

[0075] CF ３ CF = CClCF ３The content of this substance can be determined by combining mass analysis using gas chromatography / mass spectrometry (GC / MS) performed with a gas chromatograph (product name "GC-2014") manufactured by Shimadzu Corporation, and structural analysis using NMR spectroscopy (product name "400YH") manufactured by JEOL Corporation.

[0076] <C ３ F ５ HCl ２ > C ３ F ５ HCl ２ The content is between 0.0001 mol% and 3 mol%. ３ F ５ HCl ２ The lower limit of the content 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 the storage stability of the product (more specifically, the perfluoroalkene compound), C ３ F ５ HCl ２ The upper limit of the content 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 the decomposition of the product (more specifically, the perfluoroalkene compound), C ３ F ５ HCl ２ The content of is preferably 0.0001 mol% or more and 1.5 mol% or less.

[0077] C ３ F ５ HCl ２ The content of this substance can be determined by combining mass analysis using gas chromatography / mass spectrometry (GC / MS) performed with a gas chromatograph (product name "GC-2014") manufactured by Shimadzu Corporation, and structural analysis using NMR spectroscopy (product name "400YH") manufactured by JEOL Corporation.

[0078] <Applications> The composition of this embodiment can be effectively used, for example, as a raw material for the production of perfluoroalkyne compounds. Perfluoroalkyne compounds are useful, for example, as etching gases.

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

[0080] While embodiments of this disclosure have been described above, various modifications to the form and details are possible without departing from the spirit and scope of the claims.

[0081] This embodiment will be described in more detail by reference to examples. However, this embodiment is not limited by 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, the amount of aluminum chloride listed in Table 1 was added to a metal reaction vessel, and the lid was closed to create a sealed system. Then, the amount of fluorinating agent listed in Table 1 was added. In Table 1, R22 is chlorodifluoromethane (HClF). ２Next, under conditions of 25°C (room temperature) and the pressure as described in Table 1, the fluorination reaction of aluminum chloride was carried out by stirring aluminum chloride and the fluorinating agent. During this process, sampling was performed as needed to determine when the fluorination reaction was complete and when there was no change in the composition within the reaction system. Next, in cases where "Yes" was written in the "Presence or Absence of Vacuum Distillation" column of Table 1, components other than fluorinated aluminum chloride were removed by vacuum pump to reduce the pressure in the metal reaction vessel to a gauge pressure of -100 kPaG (in other words, by drying). If "No" was written in the "Presence or Absence of Vacuum Distillation" column of Table 1, it means that vacuum distillation of components other than fluorinated aluminum chloride was not performed. Based on the above, fluorinated aluminum chloride-containing catalysts for each sample were prepared.

[0084] [Correction based on Rule 91 14.05.2026] <Preparation of the first perfluoroalkene compound> Next, in the metal reaction vessel from which components other than fluorinated aluminum chloride have been removed by distillation, the amount of tetrafluoroethylene (CF) shown in Table 2 is added. ２ =CF ２ ) (i.e., the second perfluoroalkene compound) and the amount of pentafluoroethyl iodide (CF) listed in Table 2. ３ CF ２ I) (i.e., perfluoroalkyl iodide) was charged and stirred under the temperature and pressure shown in Table 1 to allow the "reaction between the second perfluoroalkene compound and the perfluoroalkyl iodide" to proceed. During this process, samples were taken as needed, and the reaction was identified as complete when there was no change in the composition within the reaction system. The composition was determined by performing mass spectrometry by gas chromatography / mass spectrometry (GC / MS) using a gas chromatograph (product name "GC-2014") manufactured by Shimadzu Corporation, and by performing structural analysis by NMR spectroscopy using an NMR (product name "400YH") manufactured by JEOL Corporation.

[0085] Based on the above, perfluoroalkene compounds of samples 1-3 and sample 11 were obtained in the form of compositions containing the first perfluoroalkene compound. Mass spectrometry by gas chromatography / mass spectrometry (GC / MS) was performed on these compositions using a gas chromatograph (product name "GC-2014") manufactured by Shimadzu Corporation, and structural analysis by NMR spectroscopy was performed using an NMR (product name "400YH") manufactured by JEOL Corporation, thereby obtaining the first perfluoroalkene compound (specifically, CF ３ -CF = CF - CF ３ The product was confirmed to have been prepared, and the conversion rate was confirmed to be as shown in Table 2. Here, the conversion rate means the ratio [%] of the total amount of substances [mol] of compounds other than the raw material compounds contained in the gas effluent from the metal reaction vessel to the amount of substance [mol] of the raw material compounds supplied to the metal reaction vessel.

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

[0087] <CF ３ CF = CClCF ３ Content of each sample > For each sample composition, use the method described in Embodiment 2 to obtain CF ３ CF = CClCF ３ The content was measured. The results obtained are shown in Table 3, "CF ３ CF = CClCF ３ Enter the value in the "[mol%]" field.

[0088] <C ３ F ５ HCl ２Content of > For each sample, the composition is prepared using the method described in Embodiment 2. ３ F ５ HCl ２ The content was measured. The results obtained are shown in Table 3, "C ３ F ５ HCl ２ Enter the value in the "[mol%]" field.

[0089]

[0090]

[0091]

[0092] The methods for producing the first perfluoroalkene compounds in Samples 1 to 3 correspond to examples. The method for producing the first perfluoroalkene compound in Sample 11 corresponds to a comparative example. It was confirmed that the methods for producing the first perfluoroalkene compounds in Samples 1 to 3 exhibit a particularly superior effect compared to the method for producing the first perfluoroalkene compound in Sample 11, enabling the acquisition of the perfluoroalkene compound in high yield. Therefore, it was found that the methods for producing the first perfluoroalkene compounds in Samples 1 to 3 enable the acquisition of the perfluoroalkene compound in high yield.

Claims

1. A method for producing a first perfluoroalkene compound, comprising the step of reacting a second perfluoroalkene compound and a perfluoroalkyl iodide in the presence of a fluorinated aluminum chloride-containing catalyst to obtain the first perfluoroalkene compound, wherein the fluorinated aluminum chloride-containing catalyst is obtained by removing at least a portion of the 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, and the perfluoroalkyl iodide is represented by formula 3. (In formula 1, R １ ~R ５ Each of these independently represents either a fluorine atom or a perfluoroalkyl group. (In formula 2, R ３ ~R ５ (This is the same as above.) (In formula 3, R １ and R ２ (This is the same as above.) 2. [Correction based on Rule 91 14.05.2026] The method for producing the first perfluoroalkene compound according to claim 1, wherein in the step, the reaction between the second perfluoroalkene compound and the perfluoroalkyl iodide is carried out in the liquid phase.

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

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

5. A composition comprising a perfluoroalkene compound, wherein the perfluoroalkene compound is represented by Formula 1, the content of the perfluoroalkene compound is 94 mol% or more, and the composition contains CF ３ CF = CClCF ３ and C ３ F ５ HCl ２ further, the content of the CF ３ CF = CClCF ３ is 0.0001 mol% or more and 3 mol% or less, and the content of the C ３ F ５ HCl ２ is 0.0001 mol% or more and 3 mol% or less. (In Formula 1, R １ to 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, and the 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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