Method for producing perfluoroalkene compounds and compositions

Abstract

This invention provides a method for producing perfluoroalkene compounds that enables the acquisition of perfluoroalkene compounds in high yield. It also provides a composition with a high content of perfluoroalkene compounds. [Solution] A method for producing a perfluoroalkene compound represented by the following formula 1, comprising the step of reacting a raw material perfluoroalkene compound with a perfluoroalkyl iodide in the presence of a fluorinated aluminum chloride-containing catalyst to obtain a perfluoroalkene compound represented by formula 1, 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 method for producing a perfluoroalkene compound represented by formula 1. TIFF2026110073000020.tif32114

Description

[Technical Field]

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

[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 is known to be a reaction in which another perfluoroalkene compound and a perfluoroalkyl iodide are reacted in the presence of a catalyst (Non-Patent Document 1). Furthermore, a catalyst produced by fluorinating aluminum chloride is known as the catalyst (Non-Patent Document 1). Examples of fluorinating agents used for fluorination include chlorofluorocarbons (hereinafter also referred to as "CFCs," for example, trichlorofluoromethane (CCl3F)) and hydrochlorofluorocarbons (hereinafter also referred to as "HCFCs," for example, chlorodifluoromethane (CHClF2)) (Patent Document 1, Non-Patent Document 1). [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] U.S. Patent No. 5157171 [Non-patent literature]

[0004] [Non-Patent Document 1] Journal of Fluorine Chemistry,102(2000),199-204 [Overview of the Initiative] [Problems that the invention aims to solve]

[0005] In a method for producing a perfluoroalkene compound, when a reaction is carried out between another perfluoroalkene compound and a perfluoroalkyl iodide using aluminum fluoride chloride obtained by fluorination with CFC as a catalyst, the perfluoroalkene compound can be produced in a relatively high yield. However, trichlorofluoromethane (CCl3F), which is common as a CFC, is difficult to obtain.

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

Means for Solving the Problems

[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; 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, The method for producing the first perfluoroalkene compound, represented by formula 3, is as follows: The perfluoroalkyl iodide is represented by formula 3. [ka] (In formula 1, R 1 ~R 5 Each of these independently represents either a fluorine atom or a perfluoroalkyl group. [ka] (In formula 2, R 3 ~R 5 (This is the same as above.) [ka] (In formula 3, R 1 and R 2 (This is the same as above.)

[0010] Item 2. The method for producing the 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 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 the removal of at least a portion of the by-product is carried out 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 above composition further comprises CF3CF=CClCF3 and C3F5HCl2, The content of CF3CF=CClCF3 is 0.0001 mol% or more and 3 mol% or less. A composition in which the content of C3F5HCl2 is 0.0001 mol% or more and 3 mol% or less. [ka] (In formula 1, R 1 ~R 5 Each of these independently represents either a fluorine atom or a perfluoroalkyl group.

[0014] Item 6. The content of CF3CF=CClCF3 is 0.0001 mol% or more and 1.5 mol% or less. 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] This disclosure provides a method for producing perfluoroalkene compounds that enables obtaining perfluoroalkene compounds in high yield. Furthermore, this disclosure also provides a composition with a high content of perfluoroalkene compounds. [Modes for carrying out the invention]

[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~B" means an upper and lower limit of a range (i.e., A or greater and B or less). If no unit is specified for A, but a unit is specified only for B, then the units for A and B are the same.

[0018] When representing a compound or the like by a chemical formula in the present disclosure, when the atomic ratio is not particularly limited, it includes all conventionally known atomic ratios and should not necessarily be limited only to those within the stoichiometric range.

[0019] [Embodiment 1: Method for Producing Perfluoroalkene Compound] A method for producing a perfluoroalkene compound according to an 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: 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 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; the perfluoroalkyl iodide is represented by Formula 3. [Chemical Formula] (In Formula 1, R 1 ~R 5 each independently represents a fluorine atom or a perfluoroalkyl group.) [Chemical Formula] (In Formula 2, R 3 ~R 5 are the same as above.) [Chemical Formula] <000019�> (In Formula 3, R 1 and R 2 are 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, using hydrochlorofluorocarbons as fluorinating agents tends to produce at least one byproduct selected from the group consisting of CHF3, CHClF2, CHCl2F, and CHCl3, in addition to fluorinated aluminum chloride. CHF3, CHClF2, CHCl2F, and CHCl3 are unstable and readily react with at least one byproduct selected from the group consisting of a second perfluoroalkene compound, a perfluoroalkyl iodide, and a first perfluoroalkene compound. As a result, such reactions tend to produce compounds other than perfluoroalkene compounds (for example, organic compounds with 3 carbon atoms other than perfluoroalkene compounds). Therefore, the yield of perfluoroalkene compounds 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 of this 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 for obtaining the first perfluoroalkene compound"). The phrase "comprising the 'step for obtaining the first perfluoroalkene compound'" means that the method may consist only of the "step for obtaining the first perfluoroalkene compound," or it may include other steps in addition to the "step for obtaining the first perfluoroalkene compound." Examples of "other steps" include "a step for 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."

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

[0025] In the step of obtaining the first perfluoroalkene compound described above, the reaction between the second perfluoroalkene compound and perfluoroethyl iodide is preferably carried out in the liquid phase. Although the yield of the perfluoroalkene compound tends to decrease when carried out in the liquid phase compared to the gas phase, according to this disclosure, it is possible to produce the perfluoroalkene compound in high yield even when carried out in the liquid phase.

[0026] The reaction mechanism of the above-mentioned "reaction between the second perfluoroalkene compound and perfluoroethyl iodide" is outlined below. [ka] Furthermore, in the above reaction mechanism, R 1 ~R 5 As will be explained later, "-IF" means de-IF reaction, and "ACF" means catalyst containing fluorinated aluminum chloride.

[0027] In the above-described "reaction of the second perfluoroalkene compound with perfluoroethyl 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] In the above-described "reaction of the second perfluoroalkene compound with perfluoroethyl 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 allows for a further improvement in 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 carried out in liquid phase, the temperature of the "reaction between the second perfluoroalkene compound and perfluoroethyl 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] When carried out in the gas phase, the temperature of the "reaction between the second perfluoroalkene compound and perfluoroethyl iodide" is preferably between 10°C and 80°C. This can further improve the yield of the perfluoroalkene compound. The temperature is more preferably between 20°C and 75°C, and even more preferably between 25°C and 70°C.

[0031] When carried out in liquid phase, the pressure of the "reaction between the second perfluoroalkene compound and perfluoroethyl 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] When carried out in the gas phase, the pressure of the "reaction of the second perfluoroalkene compound with perfluoroethyl 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] The reaction time for the "reaction of the second perfluoroalkene compound with perfluoroethyl iodide" described above is preferably 0.1 seconds to 300 seconds. This can further improve the yield of the perfluoroalkene compound. The reaction time is more preferably 0.5 seconds to 250 seconds, and even more preferably 1 second to 200 seconds.

[0034] 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 perfluoroethyl iodide" is 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. [ka] (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, R2 is a perfluoroalkyl group. Preferably, in the above formula 1, R 1 and R 3 ~R 5 One or more of the atoms are fluorine atoms, and R 2 is a perfluoroalkyl group, more preferably R 1 and R 3 ~R 5 Two or more of the atoms are fluorine atoms, and R 2 is a perfluoroalkyl group, and more preferably R 1 and R 3 ~R 5 Three or more of the atoms are fluorine atoms, and R 2 is a perfluoroalkyl group, and 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 This is a methyl group.

[0038] Examples of the first perfluorokene compounds 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, and (CF3)2C=CFC(CF3)3.

[0039] <Second perfluoroalkene compound> The second perfluoroalkene compound is represented by formula 2. [ka] (In formula 2, R 3~R 5 (This is the same as above.) This allows for a further improvement in the yield of perfluoroalkene compounds.

[0040] In Formula 2 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 2 above, the number of carbon atoms in the perfluoroalkyl group may be 1, 2, or 3.

[0041] Preferably, in formula 2 above, R 3 ~R 5 One or more of these atoms are fluorine atoms, more preferably two or more are fluorine atoms, and even more preferably all 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, and C(CF3)2=C(CF3)2. These second perfluoroalkene compounds can be used individually 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 (This is the same as above.) This allows for a further improvement in 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 formula 3 above, 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 CF3CF2I, (CF3)2CFI, and CF3I. 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 catalyst containing fluorinated aluminum chloride 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 catalyst containing fluorinated aluminum chloride, thereby improving the yield of perfluoroalkene compounds. 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 includes 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 the by-products include at least one selected from the group consisting of CHF3, CHClF2, CHCl2F, and CHCl3.

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

[0053] The amount of fluorinated aluminum chloride-containing catalyst 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] A 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 a 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 a 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] <Process for obtaining the product> In the process of obtaining the above product, the reaction of aluminum chloride in the presence of hydrochlorofluorocarbon (hereinafter also simply referred to as "the 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 in 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 in 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. A ratio of 0.1 or more and 5 or less is more preferable.

[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 between 0°C and 600°C. This makes it easier to produce fluorinated aluminum chloride, thereby improving the yield of the perfluoroalkene compound. The temperature is more preferably between 10°C and 500°C, and even more preferably between 20°C and 400°C.

[0059] When carried out in the liquid phase, the pressure of the "aluminum chloride reaction" described above is preferably between -50 kPaG and 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 between -40 kPaG and 1700 kPaG in gauge pressure, and even more preferably between 0 kPaG and 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 fluorinating agent, hydrochlorofluorocarbon) 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] <Process for obtaining a catalyst containing fluorinated aluminum chloride> It is preferable to remove at least some of the by-products at a temperature between 0°C and 200°C. This makes it easier to remove the by-products sufficiently, thereby improving the yield of the perfluoroalkene compound. It is more preferable to remove at least some of the by-products at a temperature between 5°C and 150°C.

[0063] The removal of at least some 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 some 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 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] <Application> The first perfluoroalkene compound obtained by the method for producing perfluoroalkene compounds of this embodiment can be effectively utilized 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, The perfluoroalkene compound is represented by formula 1, The content of the perfluoroalkene compound is 94 mol% or more. The composition further comprises CF3CF=CClCF3 and C3F5HCl2, The content of CF3CF=CClCF3 is between 0.0001 mol% and 3 mol%, The content of C3F5HCl2 is between 0.0001 mol% and 3 mol%. [ka] (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 compositions of this disclosure include perfluoroalkene compounds as described later. The compositions of this disclosure further include CF3CF=CClCF3 and C3F5HCl2 as described later. The compositions of this disclosure may consist of a perfluoroalkene compound, CF3CF=CClCF3, and C3F5HCl2, and may also include other components in addition to the perfluoroalkene compound, CF3CF=CClCF3, and C3F5HCl2. Examples of other components include "organic compounds having 3 carbon atoms other than the first perfluoroalkene compound" excluding C3F5HCl2. Examples of "organic compounds having 3 carbon atoms other than the first perfluoroalkene compound" include, in addition to C3F5HCl2, at least one organic compound selected from the group consisting of C3F4HCl3, C3F5H2Cl2, and C3F5H3Cl.

[0071] <Perfluoroalkene compounds> The perfluoroalkene compound content is 94 mol% or more. Therefore, the composition of this disclosure contains a high concentration of perfluoroalkene compounds, 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] <CF3CF=CClCF3> The content of CF3CF=CClCF3 is between 0.0001 mol% and 3 mol%. 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 the decomposition of the product (more specifically, the perfluoroalkene compound), the content of CF3CF=CClCF3 is preferably between 0.0001 mol% and 1.5 mol%.

[0075] The CF3CF=CClCF3 content 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] <c3f5hcl2> The content of C3F5HCl2 is between 0.0001 mol% and 3 mol%. The lower limit of the C3F5HCl2 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 storage stability of the product (more specifically, the perfluoroalkene compound), the upper limit of the C3F5HCl2 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), the C3F5HCl2 content is preferably between 0.0001 mol% and 1.5 mol%.

[0077] The C3F5HCl2 content 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] <Application> 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 manufacturing 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. [Examples]

[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 catalysts containing fluorinated aluminum chloride> The first perfluoroalkene compounds for samples 1-3 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 refers to chlorodifluoromethane (CHClF2). Next, the fluorination reaction of aluminum chloride was carried out by stirring the aluminum chloride and fluorinating agent under conditions of 25°C (room temperature) and the pressure as listed in Table 1. 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 listed 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 inside the metal reaction vessel to a gauge pressure of -100 kPaG (in other words, by drying). If "No" was listed 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] <Preparation of the first perfluoroalkene compound> Next, in the metal reaction vessel from which components other than fluorinated aluminum chloride had been distilled off, the amounts of tetrafluoroethylene (CF2=CF2) (i.e., the second perfluoroalkene compound) and the amounts of pentafluoroiodide (CF3CF2I) (i.e., perfluoroalkyl iodide) listed in Table 2 were charged, and the reaction between the second perfluoroalkene compound and perfluoroethyl iodide was carried out by stirring under the temperature and pressure conditions listed in Table 1. During this process, samples were taken as needed, and the reaction was identified as complete when there was no longer any 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 spectrometer (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 analysis 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 spectrometer (product name "400YH") manufactured by JEOL Corporation. This confirmed 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 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 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 rate of "CF3-CF=CF-CF3". The obtained results are recorded in the column of "First Perfluoroalkene Compound" in Table 3. That the content rate of the first perfluoroalkene compound is 94 mol% or more means that the perfluoroalkene compound could be obtained in a high yield.

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

[0088] <Content rate of C3F5HCl2> For the composition related to each sample, using the method described in Embodiment 2, the content rate 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 compounds in Samples 1-3 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 1-3 exhibit a particularly superior effect compared to the method for producing the first perfluoroalkene compound in Sample 11, enabling the acquisition of perfluoroalkene compounds in high yield. Therefore, it was found that the methods for producing the first perfluoroalkene compounds in Samples 1-3 enable the acquisition of perfluoroalkene compounds in high yield.

Claims

1. A method for producing a first perfluoroalkene compound, The process includes a step of reacting a second perfluoroalkene compound with a perfluoroalkyl iodide in the presence of a catalyst containing fluorinated aluminum chloride to obtain the first perfluoroalkene compound. 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 hydrochlorofluorocarbons. The first perfluoroalkene compound is represented by formula 1, The second perfluoroalkene compound is represented by formula 2, The method for producing the first perfluoroalkene compound, represented by formula 3, is as follows: The perfluoroalkyl iodide is represented by formula 3. 【Chemistry 1】 (In formula 1, R １ ~R ５ Each of these independently represents either a fluorine atom or a perfluoroalkyl group. 【Chemistry 2】 (In formula 2, R ３ ~R ５ (This is the same as above.) 【Transformation 3】 (In formula 3, R １ and R ２ (This is the same as above.)

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

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. A method for producing a 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, 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 and further contains The CF ３ CF = CClCF ３ The content is between 0.0001 mol% and 3 mol%, Said C ３ F ５ HCl ２ A composition having a content of 0.0001 mol% or more and 3 mol% or less. 【Chemistry 4】 (In formula 1, R １ ~R ５ Each of these independently represents either a fluorine atom or a perfluoroalkyl group.

6. The CF ３ CF = CClCF ３ The content is between 0.0001 mol% and 1.5 mol%, 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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