Perfluoroalkyne compound production method and composition

Abstract

A perfluoroalkyne compound production method comprising a step for reacting a perfluoroalkadiene compound in the presence of a catalyst containing fluorinated aluminium chloride to obtain a perfluoroalkyne compound, wherein the catalyst containing fluorinated aluminium chloride is obtained by removing at least some by-products from a product obtained by reacting aluminium chloride in the presence of a hydrochlorofluorocarbon.

Description

Methods for producing perfluoroalkyne compounds and compositions

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

[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 is produced by using a fluorinating agent to produce aluminum chloride (AlCl ３ It can be obtained by fluorinating (Patent Documents 1-2). Examples of fluorinating agents 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 Documents 1-2).

[0004] U.S. Patent No. 5,157,171, International Publication No. 2020 / 075728

[0005] When fluorinated aluminum chloride obtained by fluorination with CFCs is used as a catalyst for the isomerization reaction of perfluoroalkadiene compounds, perfluoroalkyne compounds can be produced in relatively high yields. However, trichlorofluoromethane (CCl), which is a common CFC, is used as a catalyst. ３ F) 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 carry out the isomerization reaction of perfluoroalkadiene compounds to 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 five carbon atoms.

[0008] This disclosure includes the following components:

[0009] Item 1. 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.

[0010] Item 2. The method for producing the perfluoroalkyne compound according to Item 1, wherein the perfluoroalkyne compound is represented by Formula 1. (In formula 1, R １ ~R ６ Each of these independently represents either a fluorine atom or a perfluoroalkyl group.

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

[0012] Item 4. The method for producing a perfluoroalkyne compound according to any one of items 1 to 3, wherein the perfluoroalkadiene compound is represented by formula 2. (In formula 2, R １ ~R ６ Each of these independently represents either a fluorine atom or a perfluoroalkyl group.

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

[0014] Item 6. A method for producing a perfluoroalkyne compound according to any one of items 1 to 5, wherein the reaction of the perfluoroalkadiene compound in the step is carried out in the liquid phase.

[0015] Item 7. A method for producing a perfluoroalkyne compound according to any one of items 1 to 6, wherein the hydrochlorofluorocarbon is one or both of trichlorofluoromethane and dichlorofluoromethane.

[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, wherein the content of the perfluoroalkyne compound is 99.5 mol% or more, and the composition further comprises 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.

[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.

[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.

[0020] Specific examples of a method for producing a perfluoroalkyne compound and a composition according to an embodiment of the present disclosure (hereinafter also referred to as "the present embodiment") will be described below.

[0021] In this specification, the notation in the form of "A to B" means the upper and lower limits of the range (that is, A or more and B or less). When there is no unit description for A and there is a unit description only for B, the units of A and B are the same.

[0022] 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.

[0023] [Embodiment 1: Method for Producing Perfluoroalkyne Compound] A method for producing a perfluoroalkyne compound according to an embodiment of the present disclosure will be described. An embodiment of the present disclosure (hereinafter also referred to as "the present embodiment") is a method for producing a perfluoroalkyne compound, which includes a step of reacting a perfluoroalkadiene compound in the presence of a catalyst containing fluorinated aluminum chloride to obtain a perfluoroalkyne compound. The catalyst containing fluorinated aluminum chloride is obtained by removing at least a part of by-products from a product obtained by reacting aluminum chloride in the presence of hydrochlorofluorocarbon.

[0024] According to the present disclosure, it is possible to provide a method for producing a perfluoroalkyne compound by an isomerization reaction of a perfluoroalkadiene compound, which enables the perfluoroalkyne compound to be obtained in a high yield. The reason is推测 as follows.

[0025] In the fluorination of aluminum chloride, when a hydrochlorofluorocarbon is used as a fluorinating agent, in addition to fluorinated aluminum chloride, at least one selected from the group consisting of CHF ３ , CHClF ２ , CHCl ２ F, and CHCl ３ is likely to be generated as a by-product. CHF３ , CHClF ２ , CHCl ２ F, and CHCl ３ Because it is unstable and readily reacts with perfluoroalkadiene compounds and / or perfluoroalkyne compounds, 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] ≪Step to obtain a perfluoroalkyne compound≫ The method for producing a perfluoroalkyne compound according to the present 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 to obtain a perfluoroalkyne compound"). "Means comprising the 'step to obtain a perfluoroalkyne compound'" means that the method may consist only of the "step to obtain a perfluoroalkyne compound," or it may include other steps in addition to the "step to obtain a perfluoroalkyne compound." Examples of "other steps" include "a 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."

[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" 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 0 kPaG to 2000 kPaG. This can further improve the yield of the perfluoroalkyne compound. The gauge pressure is more preferably 0 kPaG to 2000 kPaG, and even more preferably 50 kPaG to 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 "step for obtaining a perfluoroalkyne compound" described above, a purification treatment may be performed after the "reaction of the perfluoroalkadiene compound" is completed. The method of the purification treatment is not particularly limited, but the purification treatment may be carried out by a conventionally known method.

[0037] <Perfluoroalkyne compounds> Perfluoroalkyne compounds are preferably represented by formula 1. (In formula 1, R １ ~R ６ Each of these independently represents either a fluorine atom or a perfluoroalkyl group. This allows for a further improvement in the yield of perfluoroalkyne compounds.

[0038] 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 perfluoroalkyne compound. In Formula 1 above, the number of carbon atoms in the perfluoroalkyl group may be 1, 2, or 3.

[0039] Preferably, in the above formula 1, R １ ~R ６ 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, 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 the following and 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.

[0040] Examples of perfluoroquine compounds represented by formula 1 include CF ３ C≡CCF ３ CF ３ C≡CCF ２ CF ３ CF ３ C≡CCF(CF ３ ) ２ CF ３ C≡CC(CF３ ) ３ CF ３ CF ２ C≡CCF ２ CF ３ CF ３ CF ２ C≡CCF(CF ３ ) ２ CF ３ CF ２ C≡CC(CF ３ ) ３ (CF ３ ) ２ CFC≡CCF(CF ３ ) ２ (CF ３ ) ２ CFC≡CC(CF ３ ) ３ , and (CF ３ ) ３ CC≡CC(CF ３ ) ３ These are some examples.

[0041] <Perfluoroalkadiene Compounds> Perfluoroalkadiene compounds are preferably represented by formula 2. (In formula 2, R １ ~R ６ Each of these independently represents either a fluorine atom or a perfluoroalkyl group. This allows for a further improvement in 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 them 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, R １ ~R ３ One or more of them and R ４ ~R ５ One or more of them are fluorine atoms, more preferably, two or more of R １ ~R ３ And two or more of R ４ ~R ５ Are fluorine atoms, still more preferably, all of R １ ~R ６ Are fluorine atoms.

[0044] Examples of the perfluoroalkadiene compound represented by the formula 2 include, for example, CF ２ =CFCF=CF ２ , CF ２ =CFCF=CFCF ３ , CF ３ CF=CFCF=CFCF ３ , CF(CF ３ )=CFCF=CF ２ , C(CF ３ ) ２ =CFCF=CF ２ , CF(CF ３ )=CFCF=CF(CF ３ ), C(CF ３ ) ２ =CFCF=CF(CF ３ ), C(CF ３ ) ２ =CFCF=C(CF ３ ) ２ , CF ２ =C(CF ３ )C(CF ３ )=CF ２ And so on. These perfluoroalkadiene compounds represented by the formula 2 can be used alone or in combination of two or more.

[0045] <Fluorinated Aluminum Chloride-Containing Catalyst> The fluorinated aluminum chloride-containing catalyst is obtained by removing at least a portion of the by-products from the product obtained by reacting aluminum chloride in the presence of a fluorinating agent, hydrochlorofluorocarbon. This makes it possible to keep the by-product content in the fluorinated aluminum chloride-containing catalyst low, thereby improving the yield of the perfluoroalkyne 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".

[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 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.

[0048] 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.

[0049] The content of fluorinated aluminum chloride in the fluorinated aluminum 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 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").

[0053] <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.

[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 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] <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, and thus the yield of the perfluoroalkyne compound can be further improved. It is even more preferable to remove at least a portion of the by-products at a temperature of 5°C to 150°C.

[0061] The removal of at least a portion 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 a portion 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] <Applications> The perfluoroalkyne compounds obtained by the method for producing perfluoroalkyne compounds according to 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.

[0066] [Embodiment 2: Composition] The composition according to this embodiment will be described. This embodiment is a composition comprising a perfluoroalkyne compound, wherein the content of the perfluoroalkyne compound is 99.5 mol% or more, and the composition further comprises 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 composition of this disclosure comprises a perfluoroalkyne compound as described later. The composition of this disclosure further comprises a first organic compound as described later. The composition of this disclosure may consist of a perfluoroalkyne compound and a first organic compound, and may also contain other components in addition to the perfluoroalkyne compound and the first organic compound. Other components include, for example, C ４ F ５ HCl and C ４ F ７ One or both of H are mentioned.

[0069] C ４ F ５The HCl 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. ４ F ７ The H content is measured when the target is C ４ F ７ Except for the fact that it is H, C ４ F ５ It can be identified using a method similar to the method for measuring HCl content.

[0070] <Perfluoroalkyne Compounds> The perfluoroalkyne compound content is 99.5 mol% or more. As a result, the composition of this disclosure contains perfluoroalkyne compounds at a high concentration of 99.5 mol% or more, 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 more, 99.7 mol% or more, 99.8 mol% or more, or 99.9 mol% or more. The upper limit of the perfluoroalkyne compound content is preferably 100 mol% or less.

[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, at 0.0001 mol% or more and 0.5 mol% or less, 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 C ５ H ３ F ７ , C ５ H ３ F ６ Cl, C ５ H ２ F ６ Cl ２ , C ５ H ２ F ７ Cl, C ５ HF ７ Cl ２ , and C ５ HF ６ Cl ３ At least one compound selected from the group consisting of the following is mentioned.

[0076] <Applications> The composition 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.

[0077] <<Method for Producing 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.

[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 Fluorinated Aluminum Chloride-Containing Catalysts> Perfluoroalkyne compounds of samples 1-2, 11-12, and 101-102 were prepared as follows.

[0081] 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). ２ ) refers to dichlorofluoromethane (CHCl ２ F) refers to trichlorofluoromethane (CCl), and R11 is trichlorofluoromethane (CCl). ３This refers to F). Next, under conditions where the temperature was 25°C (room temperature) and the pressure was as shown 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 -10 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.

[0082] <Preparation of perfluoroalkyne compounds> Next, in the metal reaction vessel from which components other than fluorinated aluminum chloride have been removed by distillation, hexafluorobutadiene (CF) is added in the amount shown in Table 2. ２ =CF - CF = CF ２ By adding ) and stirring under conditions where the temperature is room temperature and the pressure is as shown in Table 2, hexafluorobutadiene (CF ２ =CF - CF = CF ２ The isomerization reaction of ) was carried out. During this process, samples were taken as needed, and the completion of the isomerization reaction was determined when there was no further change in 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.

[0083] Based on the above, perfluoroalkyne compounds were obtained in the form of compositions containing perfluoroalkyne compounds for samples 1-2, 11-12, and 101-102. 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 identifying the perfluoroalkyne compounds (specifically, hexafluoro-2-butyne (CF) ３ -C≡C-CF ３ It was confirmed that the mixture was prepared and that the conversion rate was 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.

[0084] <Content of perfluoroalkyne compounds> For each sample, using the method described in Embodiment 2, the perfluoroalkyne compound contained in the composition was found to be hexafluoro-2-butyne (CF ３ -C≡C-CF ３ )) and CF ３ -C≡C-CF ３ The content and were measured. The results obtained are recorded in the "Perfluoroalkyne Compound" column of Table 3. A perfluoroalkyne compound content of 99.5 mol% or more means that the perfluoroalkyne compound was obtained in high yield.

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

[0086] <C ４ F ５ HCl content and C ４ F ７ H content > For each sample composition, use the method described in Embodiment 2 to obtain C ４ F５ The HCl content was measured. The results obtained are shown in Table 3, under "C ４ F ５ Note in the "HCl [mol%]" column. Also, for the composition related to each sample, use the method described in Embodiment 2. ４ F ７ The H content was measured. The results obtained are shown in Table 3, "C ４ F ７ Note the value in the "H [mol%]" column. In Table 3, "ND" (Not Detectable) means that the value was below the detection limit, specifically meaning "less than 0.0001 mol%".

[0087]

[0088]

[0089]

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

Claims

1. 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.

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

3. The 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 method for producing a perfluoroalkyne compound according to any one of claims 1 to 3, wherein the perfluoroalkadiene compound is represented by formula 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. The 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-products is removed by drying the product.

9. A composition comprising a perfluoroalkyne compound, wherein the content of the perfluoroalkyne compound is 99.5 mol% or more, and the composition further comprises 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.

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.

Images