Method for producing perfluoroalkyne compounds and compositions

Abstract

The present invention provides a method for producing perfluoroalkyne compounds by isomerization reaction of perfluoroalkadiene compounds, which enables the production of perfluoroalkyne compounds in high yield. It also provides a composition having a high content of perfluoroalkyne compounds and a low content of other organic compounds with 5 carbon atoms. [Solution] A method for producing a perfluoroalkyne compound, comprising the step of reacting a perfluoroalkadiene compound in the presence of a fluorinated aluminum chloride-containing catalyst to obtain a perfluoroalkyne 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.

Description

[Technical Field]

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

[0002] Perfluoroalkyne compounds have been conventionally used in semiconductor dry etching gases, various refrigerants, foaming agents, and heat transfer media (Patent Document 2). Furthermore, a method for producing perfluoroalkyne compounds is known, which involves obtaining the perfluoroalkyne compound by an isomerization reaction of a perfluoroalkadiene compound in the presence of a catalyst (Patent Document 2).

[0003] In methods for producing perfluoroalkyne compounds, fluorinated aluminum chloride is known as a catalyst used in the isomerization reaction of perfluoroalkadiene compounds (Patent Document 2). Fluorinated aluminum chloride can be obtained by fluorinating aluminum chloride (AlCl3) using a fluorinating agent (Patent Documents 1-2). Examples of fluorinating agents 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 Documents 1-2). [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] U.S. Patent No. 5157171 [Patent Document 2] International Publication No. 2020 / 075728 [Overview of the Initiative] [Problems that the invention aims to solve]

[0005] When fluorinated aluminum chloride, obtained by fluorination using CFCs, is used as a catalyst for the isomerization reaction of perfluoroalkadiene compounds, perfluoroalkyne compounds can be produced in relatively high yields. However, trichlorofluoromethane (CCl3F), a common CFC, is difficult to obtain.

[0006] On the other hand, studies have revealed that there is room to improve the yield when using fluorinated aluminum chloride obtained by fluorination with HCFCs as a catalyst to isomerize perfluoroalkadiene compounds and produce perfluoroalkyne compounds.

[0007] This disclosure has been made in view of the above circumstances and aims to provide a method for producing a perfluoroalkyne compound by an isomerization reaction of a perfluoroalkadiene compound, which enables the production of the perfluoroalkyne compound in high yield. Furthermore, this disclosure also aims to provide a composition having a high content of the perfluoroalkyne compound and a low content of other organic compounds with 5 carbon atoms. [Means for solving the problem]

[0008] This disclosure includes the following components:

[0009] Item 1. A method for producing perfluoroalkyne compounds, The process includes reacting a perfluoroalkadiene compound with a catalyst containing fluorinated aluminum chloride to obtain a perfluoroalkyne 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 a hydrochlorofluorocarbon, and is used as a method for producing perfluoroalkyne compounds.

[0010] Item 2. The perfluoroalkyne compound is the method for producing the perfluoroalkyne compound according to Item 1, represented by Formula 1.

Chemical formula

[0015] , , , ,

[0013] , , ,

[0014] , , ,

[0016] ~R 6 each independently represents a fluorine atom or a perfluoroalkyl group.)

[0011] Item 3. In Formula 1, the number of carbon atoms of the perfluoroalkyl group is 1 or more and 3 or less. The method for producing the perfluoroalkyne compound according to Item 2.

[0012] Item 4. The perfluoroalkadiene compound is the method for producing the perfluoroalkyne compound according to any one of Items 1 to 3, represented by Formula 2.

Chemical formula

[0013] Item 5. In Formula 2, the number of carbon atoms of the perfluoroalkyl group is 1 or more and 3 or less. The method for producing the perfluoroalkyne compound according to Item 4.

[0014] Item 6. In the above step, the reaction of the perfluoroalkadiene compound is carried out in the liquid phase. The method for producing the perfluoroalkyne compound according to any one of Items 1 to 5.

[0015] Item 7. The hydrochlorofluorocarbon is one or both of trichlorofluoromethane and dichlorodifluoromethane. The method for producing the perfluoroalkyne compound according to any one of Items 1 to 6.

[0016] Item 8. A method for producing a perfluoroalkyne compound according to any one of items 1 to 7, wherein the removal of at least a portion of the by-product is carried out by drying the product.

[0017] Item 9. A composition comprising a perfluoroalkyne compound, The content of the perfluoroalkyne compound is 99.5 mol% or more. The composition further comprises a first organic compound, The first organic compound has 5 carbon atoms. A composition in which the content of the first organic compound is 0.0001 mol% or more and 0.5 mol% or less.

[0018] Item 10. The composition according to item 9, wherein the content of the first organic compound is 0.0001 mol% or more and 0.2 mol% or less. [Effects of the Invention]

[0019] According to this disclosure, a method for producing a perfluoroalkyne compound by an isomerization reaction of a perfluoroalkadiene compound is available, which enables the production of the perfluoroalkyne compound in high yield. Furthermore, according to this disclosure, a composition is also available which has a high content of the perfluoroalkyne compound and a low content of organic compounds other than the perfluoroalkyne compound that have 5 carbon atoms. [Modes for carrying out the invention]

[0020] A specific example of a method for producing a perfluoroalkyne compound and a composition according to one embodiment of this disclosure (hereinafter also referred to as "this embodiment") is described below.

[0021] 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.

[0022] 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.

[0023] [Embodiment 1: Method for producing perfluoroalkyne compounds] A method for producing a perfluoroalkyne compound according to one embodiment of this disclosure will be described. One embodiment of the present disclosure (hereinafter also referred to as "this embodiment") is a method for producing a perfluoroalkyne compound, comprising the step of reacting a perfluoroalkadiene compound in the presence of a fluorinated aluminum chloride-containing catalyst to obtain a perfluoroalkyne 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.

[0024] According to this disclosure, it is possible to provide a method for producing perfluoroalkyne compounds by isomerization reaction of perfluoroalkadiene compounds, which enables the production of perfluoroalkyne compounds in high yield. The reason for this is presumed to be as follows.

[0025] When hydrochlorofluorocarbons are used as fluorinating agents 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 readily react with perfluoroalkadiene compounds and / or perfluoroalkyne compounds. As a result, such reactions tend to produce compounds other than perfluoroalkyne compounds (for example, organic compounds with 5 carbon atoms other than perfluoroalkyne compounds). Therefore, the yield of perfluoroalkyne compounds may be low in such production methods.

[0026] In the method for producing perfluoroalkyne compounds 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 perfluoroalkadiene compound is suppressed, making it difficult to produce compounds other than the perfluoroalkyne compound. Consequently, the yield of the perfluoroalkyne compound can be improved.

[0027] <<Process for obtaining perfluoroalkyne compounds>> The method for producing a perfluoroalkyne compound according to this disclosure comprises the step of reacting a perfluoroalkadiene compound in the presence of a fluorinated aluminum chloride-containing catalyst to obtain a perfluoroalkyne compound (hereinafter also simply referred to as the "step for obtaining a perfluoroalkyne compound"). The phrase "comprising the 'step for obtaining a perfluoroalkyne compound'" means that the method may consist only of the "step for obtaining a perfluoroalkyne compound," or it may include other steps in addition to the "step for obtaining a perfluoroalkyne 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."

[0028] In the process of obtaining the perfluoroalkyne compound described above, the reaction of the perfluoroalkadiene compound may be carried out in the liquid phase or in the gas phase. "Reaction of the perfluoroalkadiene compound" carried out in the liquid phase refers to subjecting a liquid perfluoroalkadiene compound to an isomerization reaction. "Reaction of the perfluoroalkadiene compound" carried out in the gas phase refers to subjecting a gaseous perfluoroalkadiene compound to an isomerization reaction. When carried out in the liquid phase, the reaction of the perfluoroalkadiene compound 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 of the perfluoroalkadiene compound may be in batch mode or flow mode (continuous mode), but is preferably in flow mode.

[0029] In the process of obtaining the above-mentioned perfluoroalkyne compound, the reaction of the perfluoroalkadiene compound is preferably carried out in the liquid phase. Although the yield of the perfluoroalkyne 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 perfluoroalkyne compound in high yield even when carried out in the liquid phase.

[0030] In the "reaction of perfluoroalkadiene compounds" described above, the ratio M2 / M1 of the amount of fluorinated aluminum chloride in the aluminum chloride-containing catalyst to the amount of perfluoroalkadiene compound M1 is preferably 0.0001 or more and 2 or less. This can further improve the yield of the perfluoroalkyne compound. The ratio M2 / M1 is more preferably 0.0001 or more and 2 or less, and even more preferably 0.001 or more and 1 or less.

[0031] When carried out in liquid phase, the temperature of the "reaction of perfluoroalkadiene compounds" is preferably between 0°C and 100°C. This can further improve the yield of the perfluoroalkyne compound. The temperature is more preferably between 0°C and 100°C, and even more preferably between 10°C and 50°C.

[0032] When carried out in the gas phase, the temperature of the "reaction of perfluoroalkadiene compounds" is preferably between 0°C and 400°C. This can further improve the yield of the perfluoroalkyne compound. The temperature is more preferably between 0°C and 400°C, and even more preferably between 20°C and 300°C.

[0033] When carried out in liquid phase, the pressure of the "reaction of perfluoroalkadiene compounds" described above is preferably 0 kPaG to 2000 kPaG in gauge pressure. This can further improve the yield of the perfluoroalkyne compound. The pressure is more preferably 0 kPaG to 2000 kPaG in gauge pressure, and even more preferably 50 kPaG to 1000 kPaG.

[0034] When carried out in the gas phase, the gauge pressure for the "reaction of perfluoroalkadiene compounds" is preferably between 0 kPaG and 2000 kPaG. This can further improve the yield of the perfluoroalkyne compound. The gauge pressure is more preferably between 0 kPaG and 2000 kPaG, and even more preferably between 50 kPaG and 1000 kPaG.

[0035] The reaction time for the perfluoroalkadiene compound (in other words, the contact time between the perfluoroalkadiene compound and the fluorinated aluminum chloride-containing catalyst) is preferably 0.1 seconds or more and 120 seconds or less. This can further improve the yield of the perfluoroalkyne compound. The time is more preferably 0.1 seconds or more and 120 seconds or less, and even more preferably 1 second or more and 75 seconds or less.

[0036] In the above-mentioned "step of obtaining a perfluoroalkyne compound", after the above-mentioned "reaction of the perfluoroalkadiene compound" is completed, a purification treatment may be carried out. The method of the purification treatment is not particularly limited, and the purification treatment may be carried out by a conventionally known method.

[0037] <Perfluoroalkyne compound> The perfluoroalkyne compound is preferably represented by Formula 1.

Chemical formula

[0038] In the above Formula 1, the number of carbon atoms of the perfluoroalkyl group is preferably 1 or more and 3 or less. Thereby, the yield of the perfluoroalkyne compound can be further improved. In the above Formula 1, the number of carbon atoms of the perfluoroalkyl group may be 1, may be 2, or may be 3.

[0039] Preferably, in the above Formula 1, one or more of R 1 ~R 6 are fluorine atoms, more preferably, two or more of them are fluorine atoms, still more preferably, three or more of them are fluorine atoms, even more preferably, four or more of them are fluorine atoms, particularly preferably, five or more of them are fluorine atoms, and most preferably, all of them are fluorine atoms. Also, preferably, in the above Formula 1, one or more of R 1 ~R 3 and one or more of R 4 ~R 5 are fluorine atoms, more preferably, two or more of R 1 ~R 3 and two or more of R 4 ~R 5Two or more of the atoms are fluorine atoms, and more preferably, R 1 ~R 6 All of them are fluorine atoms.

[0040] Examples of perfluoroquine compounds represented by Formula 1 include CF3C≡CCF3, CF3C≡CCF2CF3, CF3C≡CCF(CF3)2, CF3C≡CC(CF3)3, CF3CF2C≡CCF2CF3, CF3CF2C≡CCF(CF3)2, CF3CF2C≡CC(CF3)3, (CF3)2CFC≡CCF(CF3)2, (CF3)2CFC≡CC(CF3)3, and (CF3)3CC≡CC(CF3)3.

[0041] <Perfluoroalkadiene compounds> The perfluoroalkadiene compound is preferably represented by formula 2. [ka] (In formula 2, R 1 ~R 6 Each of these independently represents either a fluorine atom or a perfluoroalkyl group. This can further improve the yield of perfluoroalkyne compounds.

[0042] 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 perfluoroalkyne compound. In Formula 2 above, the number of carbon atoms in the perfluoroalkyl group may be 1, 2, or 3.

[0043] Preferably, in the above formula 1, R 1 ~R 6One 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, even more preferably four or more are fluorine atoms, particularly preferably five or more are fluorine atoms, and most preferably all are fluorine atoms. Also preferably, in the above formula 1, R 1 ~R 3 One or more of the following and R 4 ~R 5 One or more of the atoms are fluorine atoms, and more preferably, R 1 ~R 3 Any two or more of R 4 ~R 5 Two or more of the atoms are fluorine atoms, and more preferably, R 1 ~R 6 All of them are fluorine atoms.

[0044] Examples of perfluoroalkadiene compounds represented by formula 2 include CF2=CFCF=CF2, CF2=CFCF=CFCF3, CF3CF=CFCF=CFCF3, CF(CF3)=CFCF=CF2, C(CF3)2=CFCF=CF2, CF(CF3)=CFCF=CF(CF3), C(CF3)2=CFCF=CF(CF3), C(CF3)2=CFCF=C(CF3), CF2=C(CF3)C(CF3)=CF2, and so on. These perfluoroalkadiene compounds represented by formula 2 can be used individually or in combination of two or more types.

[0045] <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 reduces the by-product content in the catalyst containing fluorinated aluminum chloride, thereby improving the yield of perfluoroalkyne 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."

[0046] The above-mentioned hydrochlorofluorocarbon is preferably one or both of trichlorofluoromethane and dichlorofluoromethane. This can further improve the yield of the perfluoroalkyne compound.

[0047] 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.

[0048] Examples of the by-products include at least one selected from the group consisting of CHF3, CHClF2, CHCl2F, and CHCl3.

[0049] The content of aluminum fluoride chloride in the aluminum fluoride chloride-containing catalyst is preferably 0.1% by mass or more and 100% by mass or less. This can further improve the yield of the perfluoroalkyne 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.

[0050] The content of fluorinated aluminum chloride in a catalyst containing fluorinated aluminum chloride can be determined by energy-dispersive X-ray fluorescence analysis (EDX).

[0051] 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 perfluoroalkadiene 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.

[0052] 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 perfluoroalkyne 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 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").

[0053] <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.

[0054] 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 perfluoroalkyne compound. The ratio m2 / m1 is more preferably 0.01 or more and 10 or less, and even more preferably 0.1 or more and 5 or less.

[0055] When carried out in liquid phase, the temperature of the "aluminum chloride reaction" described above is preferably between -40°C and 100°C. This makes it easier to produce fluorinated aluminum chloride, thereby improving the yield of the perfluoroalkyne compound. The temperature is more preferably between -40°C and 100°C, and even more preferably between -20°C and 80°C.

[0056] When carried out in the gas phase, the temperature of the "aluminum chloride reaction" described above is preferably between 0°C and 500°C. This makes it easier to produce fluorinated aluminum chloride, thereby improving the yield of the perfluoroalkyne compound. The temperature is more preferably between 0°C and 500°C, and even more preferably between 20°C and 400°C.

[0057] 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 perfluoroalkyne compound. The pressure is more preferably between 0 kPaG and 1500 kPaG in gauge pressure. The lower limit of the pressure may be -50 kPaG, 0 kPaG, 50 kPaG, 100 kPaG, 150 kPaG, or 200 kPaG.

[0058] 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 perfluoroalkyne compound. The pressure is more preferably 10 kPaG to 1000 kPaG in gauge pressure. The lower limit of the pressure may be 0 kPaG, 50 kPaG, 100 kPaG, 150 kPaG, or 200 kPaG.

[0059] 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 perfluoroalkyne compound. More preferably, this time is 1 second or more and 75 seconds or less.

[0060] <Process for obtaining a catalyst containing fluorinated aluminum chloride> It is preferable to carry out the removal of 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 perfluoroalkyne compound. It is more preferable to carry out the removal of at least some of the by-products at a temperature between 5°C and 150°C.

[0061] The removal of at least some of the by-products is preferably carried out at a gauge pressure of -101.3 kPaG to 0 kPaG. This makes it easier to remove the by-products sufficiently, thereby improving the yield of the perfluoroalkyne compound. The removal of at least some of the by-products is more preferably carried out at a gauge pressure of -101.3 kPaG to -10 kPaG.

[0062] 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 perfluoroalkyne 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.

[0063] At least a portion of the by-products is preferably removed by drying the product. This can further improve the yield of the perfluoroalkyne compound. The method of drying the product is not particularly limited, but drying may be carried out, for example, by "reduced pressure".

[0064] 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.

[0065] <Application> The perfluoroalkyne compounds obtained by the method for producing perfluoroalkyne compounds according to 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.

[0066] [Embodiment 2: Composition] The composition according to this embodiment will be described. This embodiment is a composition containing a perfluoroalkyne compound, wherein the content of the perfluoroalkyne compound is 99.5 mol% or more, and the composition further contains a first organic compound, wherein the number of carbon atoms in the first organic compound is 5, and the content of the first organic compound is 0.0001 mol% or more and 0.5 mol% or less.

[0067] According to this disclosure, it is possible to provide a composition having a high content of perfluoroalkyne compounds and a low content of organic compounds other than perfluoroalkyne compounds that have 5 carbon atoms.

[0068] ≪Composition≫ The compositions of this disclosure include perfluoroalkyne compounds as described below. The compositions of this disclosure further include a first organic compound as described below. The compositions of this disclosure may consist of a perfluoroalkyne compound and a first organic compound, and may also include other components in addition to the perfluoroalkyne compound and the first organic compound. Examples of other components include one or both of C4F5HCl and C4F7H.

[0069] The C4F5HCl 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. The C4F7H content can be determined using the same method as for the C4F5HCl content, except that the target of measurement is C4F7H.

[0070] <Perfluoroalkyne compounds> The perfluoroalkyne compound content is 99.5 mol% or higher. Therefore, the composition of this disclosure contains a high concentration of perfluoroalkyne compound, 99.5 mol% or higher, making it possible to provide a composition with a high perfluoroalkyne compound content. The lower limit of the perfluoroalkyne compound content is preferably 99.6 mol% or higher, 99.7 mol% or higher, 99.8 mol% or higher, or 99.9 mol% or higher. The upper limit of the perfluoroalkyne compound content is preferably 100 mol% or lower.

[0071] The content of perfluoroalkyne compounds 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.

[0072] Since the perfluoroalkyne compound according to this embodiment is the same as the perfluoroalkyne compound according to Embodiment 1, its description will be omitted here.

[0073] <First organic compound> The first organic compound has 5 carbon atoms, and its content is 0.0001 mol% or more and 0.5 mol% or less. This allows the content of the first organic compound to be kept low, between 0.0001 mol% and 0.5 mol%, making it possible to provide a composition with a low content of organic compounds other than perfluoroalkyne compounds that have 5 carbon atoms. The lower limit of the content of the first organic compound may be 0.001 mol% or more, 0.01 mol% or more, 0.03 mol% or more, 0.07 mol% or more, or 0.1 mol% or more. The upper limit of the content of the first organic compound may be 0.4 mol% or less, 0.3 mol% or less, or 0.2 mol% or less. Preferably, the content of the first organic compound is 0.0001 mol% or more and 0.2 mol% or less.

[0074] The content of the first organic compound 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.

[0075] Examples of the first organic compound include at least one compound selected from the group consisting of C5H3F7, C5H3F6Cl, C5H2F6Cl2, C5H2F7Cl, C5HF7Cl2, and C5HF6Cl3.

[0076] <Application> The composition of this embodiment can be effectively used, for example, in applications such as etching gases. Etching gases are useful for forming cutting-edge microstructures in semiconductors, liquid crystals, and the like.

[0077] ≪Method for manufacturing the composition≫ The composition of this embodiment can be produced, for example, by the method for producing perfluoroalkyne compounds described in Embodiment 1.

[0078] 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]

[0079] This embodiment will be described in more detail by reference to examples. However, this embodiment is not limited by these examples.

[0080] <<Preparation of perfluoroalkyne compounds>> <Preparation of catalysts containing fluorinated aluminum chloride> Perfluoroalkyne compounds were prepared for samples 1-2, 11-12, and 101-102 as follows.

[0081] First, the amount of aluminum chloride listed in Table 1 was added to a metal reaction vessel, and after sealing it with a lid, the amount of fluorinating agent listed in Table 1 was added. In Table 1, R22 refers to chlorodifluoromethane (CHClF2), R21 refers to dichlorofluoromethane (CHCl2F), and R11 refers to trichlorofluoromethane (CCl3F). Next, under conditions of a temperature of 25°C (room temperature) and the pressure as listed in Table 1, the fluorination reaction of aluminum chloride was carried out by stirring the aluminum chloride and 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 indicated 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 -10 kPaG (in other words, by drying). In Table 1, the entry "None" in the "Presence or Absence of Vacuum Distillation" column means that vacuum distillation of components other than fluorinated aluminum chloride was not performed. Based on the above, fluorinated aluminum chloride-containing catalysts were prepared for each sample.

[0082] <Preparation of perfluoroalkyne compounds> Next, hexafluorobutadiene (CF2=CF-CF=CF2) was charged in the amount specified in Table 2 into the metal reaction vessel from which components other than fluorinated aluminum chloride had been distilled off. The isomerization reaction of hexafluorobutadiene (CF2=CF-CF=CF2) was carried out by stirring under conditions of room temperature and pressure as specified in Table 2. During this process, samples were taken as needed, and the completion of the isomerization reaction was determined when there was no longer any change in the composition within the reaction system. The composition was determined by mass spectrometry by gas chromatography / mass spectrometry (GC / MS) using a gas chromatograph (product name "GC-2014") manufactured by Shimadzu Corporation, and by structural analysis by NMR spectroscopy using an NMR spectrometer (product name "400YH") manufactured by JEOL Corporation.

[0083] As described above, perfluoroalkyne compounds of Sample 1-2, Sample 11-12, and Sample 101-102 were obtained in the form of a composition containing a perfluoroalkyne compound. For this composition, gas chromatography / mass spectrometry (GC / MS) was performed using a gas chromatograph (trade name "GC-2014") manufactured by Shimadzu Corporation, and structural analysis was performed by NMR spectrum using an NMR (trade name "400YH") manufactured by JEOL Ltd. As a result, it was confirmed that a perfluoroalkyne compound (specifically, hexafluoro-2-butyne (CF3-C≡C-CF3)) was produced, and the conversion rate was as described in Table 2. Here, the conversion rate means the ratio [%] of the total amount of substances [mol] of compounds other than the raw material compound contained in the effluent gas from the metal reaction vessel to the amount of substance [mol] of the raw material compound supplied to the metal reaction vessel.

[0084] <Content rate of perfluoroalkyne compound> For the composition according to each sample, using the method described in Embodiment 2, it was measured that the perfluoroalkyne compound contained in the composition was hexafluoro-2-butyne (CF3-C≡C-CF3)) and the content rate of CF3-C≡C-CF3. The obtained results are described in the column of "Perfluoroalkyne compound" in Table 3. That the content rate of the perfluoroalkyne compound is 99.5 mol% or more means that the perfluoroalkyne compound could be obtained in a high yield.

[0085] <Content rate of the first organic compound> For the composition according to each sample, using the method described in Embodiment 2, the content rate of the first organic compound was measured. The obtained results are described in the column of "First organic compound [mol%]" in Table 3.

[0086] <Content rates of C4F5HCl and C4F7H> For each sample composition, the C4F5HCl content was measured using the method described in Embodiment 2. The results are recorded in the "C4F5HCl [mol%]" column of Table 3. Furthermore, for each sample composition, the C4F7H content was measured using the method described in Embodiment 2. The results are recorded in the "C4F7H [mol%]" column of Table 3. In Table 3, "ND" (Not Detectable) means that the content was below the detection limit, specifically "less than 0.0001 mol%".

[0087] [Table 1]

[0088] [Table 2]

[0089] [Table 3]

[0090] The methods for producing perfluoroalkyne compounds in Samples 1 and 2 correspond to examples. The methods for producing perfluoroalkyne compounds in Samples 11 and 12 correspond to comparative examples. The methods for producing perfluoroalkyne compounds in Samples 101 and 102 correspond to reference examples. It was confirmed that the methods for producing perfluoroalkyne compounds in Samples 1 and 2 exhibit a particularly superior effect compared to the methods for producing perfluoroalkyne compounds in Samples 11 and 12, enabling the acquisition of perfluoroalkyne compounds in high yield. Therefore, it was found that the methods for producing perfluoroalkyne compounds in Samples 1 and 2 enable the acquisition of perfluoroalkyne compounds in high yield.

Claims

1. A method for producing perfluoroalkyne compounds, The process includes reacting a perfluoroalkadiene compound with a catalyst containing fluorinated aluminum chloride to obtain a perfluoroalkyne 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 a hydrochlorofluorocarbon, and is used as a method for producing perfluoroalkyne compounds.

2. The method for producing the perfluoroalkyne compound according to claim 1, which is represented by formula 1. 【Chemistry 1】 (In formula 1, R １ ~R ６ Each of these independently represents either a fluorine atom or a perfluoroalkyl group.

3. A method for producing a perfluoroalkyne compound according to claim 2, wherein the number of carbon atoms in the perfluoroalkyl group in formula 1 is 1 or more and 3 or less.

4. The perfluoroalkadiene compound is represented by formula 2, the method for producing a perfluoroalkyne compound according to any one of claims 1 to 3. 【Chemistry 2】 (In formula 2, R １ ~R ６ Each of these independently represents either a fluorine atom or a perfluoroalkyl group.

5. The method for producing a perfluoroalkyne compound according to claim 4, wherein the number of carbon atoms in the perfluoroalkyl group in formula 2 is 1 or more and 3 or less.

6. A method for producing a perfluoroalkyne compound according to any one of claims 1 to 3, wherein in the step described above, the reaction of the perfluoroalkadiene compound is carried out in the liquid phase.

7. The method for producing a perfluoroalkyne compound according to any one of claims 1 to 3, wherein the hydrochlorofluorocarbon is one or both of trichlorofluoromethane and dichlorofluoromethane.

8. A method for producing a perfluoroalkyne compound according to any one of claims 1 to 3, wherein at least a portion of the by-product is removed by drying the product.

9. A composition comprising a perfluoroalkyne compound, The content of the perfluoroalkyne compound is 99.5 mol% or more. The composition further comprises a first organic compound, The first organic compound has 5 carbon atoms. A composition in which the content of the first organic compound is 0.0001 mol% or more and 0.5 mol% or less.

10. The composition according to claim 9, wherein the content of the first organic compound is 0.0001 mol% or more and 0.2 mol% or less.

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