Method for producing purified fluoroalkyne compounds, fluorinated adsorbent, and method for producing the same.

Abstract

The present invention provides a method for producing purified fluoroalkyne compounds, a fluorinated adsorbent, and a method for producing the same, which enable the suppression of the generation of organic compounds other than the fluoroalkyne compound that originate from the fluoroalkyne compound during the dehydration treatment of the fluoroalkyne compound. [Solution] A method for producing a purified fluoroalkyne compound, comprising the step of performing a dehydration treatment on a water-containing fluoroalkyne compound using a fluorinated adsorbent to obtain a purified fluoroalkyne compound, wherein the fluoroalkyne compound is represented by formula 1. TIFF2026110074000013.tif12114 (In the formula, R 1 and R 2 Each of these independently represents a hydrogen atom, a fluorine atom, or a fluoroalkyl group, R 1 and R 2 At least one of them represents the fluoroalkyl group.

Description

[Technical Field]

[0001] This disclosure relates to a method for producing purified fluoroalkyne compounds, a fluorinated adsorbent, and a method for producing the same. [Background technology]

[0002] Conventionally, a method for purifying fluorinated hydrocarbon compounds such as hexafluorobutadiene, octafluorocyclobutane, and octafluorocyclopentene has been known, which involves dehydration treatment using an adsorbent (Patent Documents 1-3). Zeolites and boron oxide are known adsorbents used in the dehydration treatment (Patent Documents 1-3). [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] U.S. Patent No. 6544319 [Patent Document 2] Korean Patent Publication No. 2023-0134179 [Patent Document 3] International Publication No. 2007 / 063938 [Overview of the Initiative] [Problems that the invention aims to solve]

[0004] Conventionally, fluoroalkyne compounds, which are fluorinated hydrocarbons, have been used in semiconductor dry etching gases, various refrigerants, foaming agents, and heat transfer media. Regarding fluoroalkyne compounds, studies have revealed that when dehydration treatment is performed using an adsorbent as is as a purification method, the adsorbent and the fluoroalkyne compound react, easily generating organic compounds other than the fluoroalkyne compound derived from the fluoroalkyne compound, making it difficult to obtain fluoroalkyne compounds in high purity.

[0005] The present disclosure has been made in view of the above circumstances, and an object thereof is to provide a method for producing a purified fluoroalkyne compound, a fluorinated adsorbent, and a method for producing the same, which make it possible to suppress the generation of organic compounds other than the fluoroalkyne compound derived from the fluoroalkyne compound in the dehydration treatment of the fluoroalkyne compound.

Means for Solving the Problems

[0006] The present disclosure includes the following configurations.

[0007] Item 1. A step of obtaining a purified fluoroalkyne compound by performing a dehydration treatment on a fluoroalkyne compound containing water using a fluorinated adsorbent. [[ID=]14] The fluoroalkyne compound is a method for producing a purified fluoroalkyne compound represented by Formula 1.

Chemical Formula

[0008] ,

[0010] , , , , , ,

[0009] and R 2 each independently represents a hydrogen atom, a fluorine atom, or a fluoroalkyl group, and at least one of R 1 and R 2 represents the fluoroalkyl group.) 3]

[0008] Item 2. The method for producing a purified fluoroalkyne compound according to Item 1, wherein the fluorine atom content in the fluorinated adsorbent is 1 atm% or more.

[0009] Item 3. The method for producing a purified fluoroalkyne compound according to Item 1 or Item 2, wherein the fluorinated adsorbent is a fluorinated zeolite adsorbent.

[0010] Item 4. The method for producing a purified fluoroalkyne compound according to any one of Items 1 to 3, wherein the fluoroalkyl group is a CF3 group, a C2F5 group, a C3F7 group, or a C4F9 group.

[0011] Item 5. A method for producing a fluorinated adsorbent, comprising a step of treating the surface of the adsorbent with a fluorinating agent.

[0012] Item 6. The method for producing a fluorinated adsorbent according to Item 5, wherein the adsorbent is a zeolite adsorbent.

[0013] Item 7. The fluorinating agent is at least one selected from the group consisting of hydrogen fluoride, fluorine, chlorodifluoromethane, dichlorofluoromethane, and fluoroalkyne compounds, The fluoroalkyne compound is represented by Formula 2. The method for producing a fluorinated adsorbent according to Item 5 or Item 6.

Chemical formula

[0014] Item 8. The method for producing a fluorinated adsorbent according to Item 7, wherein the fluoroalkyl group is a CF3 group, a C2F5 group, a C3F7 group, or a C4F9 group.

[0015] Item 9. A fluorinated adsorbent for dehydrating a fluoroalkyne compound, The fluoroalkyne compound is represented by Formula 1. The fluorinated adsorbent.

Chemical formula

[0016] Item 10. The fluorinated adsorbent according to item 9, wherein the fluorine atom content in the fluorinated adsorbent is 1 atm% or more.

[0017] Item 11. The fluorinated adsorbent according to item 9 or 10, wherein the fluorinated adsorbent is a fluorinated zeolite adsorbent.

[0018] Item 12. The fluorinated adsorbent according to any one of items 9 to 11, wherein the fluoroalkyl group is a CF3 group, a C2F5 group, a C3F7 group, or a C4F9 group. [Effects of the Invention]

[0019] According to this disclosure, it is possible to provide a method for producing a purified fluoroalkyne compound, a fluorinated adsorbent, and a method for producing the same, which makes it possible to suppress the generation of organic compounds other than the fluoroalkyne compound that originate from the fluoroalkyne compound during the dehydration treatment of the fluoroalkyne compound. [Modes for carrying out the invention]

[0020] A method for producing a purified fluoroalkyne compound, a fluorinated adsorbent, and a specific example of the method for producing the same, according to one embodiment of the present disclosure (hereinafter also referred to as "this embodiment"), will be described below.

[0021] In this specification, the notation "A~B" means an upper and lower limit of a range (i.e., greater than or equal to A and less than or equal to B). 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 purified fluoroalkyne compounds] A method for producing a purified fluoroalkyne compound according to one embodiment of this disclosure will be described. One embodiment of the present disclosure (hereinafter also referred to as "this embodiment") comprises a step of obtaining a purified fluoroalkyne compound by performing a dehydration treatment on a water-containing fluoroalkyne compound using a fluorinated adsorbent, The fluoroalkyne compound is a method for producing a purified fluoroalkyne compound represented by Formula 1. [ka] (In formula 1, R 1 and R 2 Each of these independently represents a hydrogen atom, a fluorine atom, or a fluoroalkyl group, R 1 and R 2 At least one of them represents the fluoroalkyl group.

[0024] According to this disclosure, it is possible to provide a method for producing purified fluoroalkyne compounds that suppresses the generation of organic compounds other than the fluoroalkyne compound derived from the fluoroalkyne compound during the dehydration treatment of the fluoroalkyne compound. The reason for this is presumed to be as follows.

[0025] (a) When a fluoroalkyne compound containing water and represented by the above formula 1 is subjected to a dehydration treatment using an adsorbent as is, the adsorbent and the fluoroalkyne compound react to easily produce an organic compound other than the fluoroalkyne compound derived from the fluoroalkyne compound (for example, C4F7H when the fluoroalkyne compound is hexafluoro-2-butyne).

[0026] (b) In the method for producing the purified fluoroalkyne compound according to this embodiment, a dehydration treatment is performed using a fluorinated adsorbent. This suppresses the activity of active sites in the adsorbent, making it less likely for organic compounds other than the fluoroalkyne compound to be generated from the fluoroalkyne compound.

[0027] ≪Process for obtaining purified fluoroalkyne compounds≫ The method for producing a purified fluoroalkyne compound according to this disclosure comprises a step of obtaining a purified fluoroalkyne compound by performing a dehydration treatment on a water-containing fluoroalkyne compound using a fluorinated adsorbent (hereinafter also simply referred to as the "step of obtaining a purified fluoroalkyne compound"). The phrase "comprising the 'step of obtaining a purified fluoroalkyne compound'" means that the method may consist only of the "step of obtaining a purified fluoroalkyne compound," or it may include other steps in addition to the "step of obtaining a purified fluoroalkyne compound." Examples of "other steps" include the "step of obtaining a fluorinated adsorbent," which will be described later.

[0028] In the "step for obtaining a purified fluoroalkyne compound" described above, the "dehydration treatment of the water-containing fluoroalkyne compound using a fluorinated adsorbent" (hereinafter also simply referred to as "dehydration treatment") may be carried out in the liquid phase or in the gas phase. Dehydration treatment carried out in the liquid phase means subjecting a liquid "water-containing fluoroalkyne compound" to the dehydration treatment. Dehydration treatment carried out in the gas phase means subjecting a gaseous "water-containing fluoroalkyne compound" to the dehydration treatment. When carried out in the liquid phase, the above dehydration treatment may be carried out in a batch manner or in a flow manner (continuous manner), but it is preferable to carry it out in a batch manner. When carried out in the gas phase, the above dehydration treatment may be carried out in a batch manner or in a flow manner (continuous manner), but it is preferable to carry it out in a flow manner (continuous manner).

[0029] In the "step for obtaining a purified fluoroalkyne compound" described above, it is preferable that the amount of fluorinated adsorbent per 100 parts by mass of the fluoroalkyne compound containing water is 0.01 parts by mass or more and 200 parts by mass or less. This makes it easier to suppress the generation of organic compounds other than the fluoroalkyne compound that originate from the fluoroalkyne compound during the dehydration treatment of the fluoroalkyne compound. It is more preferable that the amount of fluorinated adsorbent per 100 parts by mass of the fluoroalkyne compound containing water is 0.05 parts by mass or more and 150 parts by mass or less, and even more preferable that it is 0.1 parts by mass or more and 100 parts by mass or less.

[0030] When carried out in the liquid phase, the temperature of the dehydration treatment is preferably between -50°C and 100°C. This makes it easier to suppress the generation of organic compounds other than the fluoroalkyne compound that originate from the fluoroalkyne compound during the dehydration treatment of the fluoroalkyne compound. The temperature is more preferably between -20°C and 75°C, and even more preferably between 0°C and 50°C.

[0031] When carried out in the gas phase, the temperature of the dehydration treatment is preferably between -10°C and 100°C. This makes it easier to suppress the generation of organic compounds other than the fluoroalkyne compound that originate from the fluoroalkyne compound during the dehydration treatment of the fluoroalkyne compound. The temperature is more preferably between 0°C and 75°C, and even more preferably between 10°C and 50°C.

[0032] When carried out in the liquid phase, the pressure of the dehydration treatment is preferably between -30 kPaG and 3200 kPaG in gauge pressure. This makes it easier to suppress the generation of organic compounds other than the fluoroalkyne compound that originate from the fluoroalkyne compound during the dehydration treatment of the fluoroalkyne compound. The pressure is more preferably between 0 kPaG and 2000 kPaG in gauge pressure, and even more preferably between 100 kPaG and 1100 kPaG.

[0033] When carried out in the gas phase, the pressure of the above dehydration treatment is preferably 0 kPaG to 3000 kPaG in gauge pressure. This makes it easier to suppress the generation of organic compounds other than the fluoroalkyne compound that originate from the fluoroalkyne compound during the dehydration treatment of the fluoroalkyne compound. The pressure is more preferably 10 kPaG to 2000 kPaG in gauge pressure, and even more preferably 20 kPaG to 1500 kPaG.

[0034] The time for the above dehydration treatment (in other words, the contact time between the water-containing fluoroalkyne compound and the fluorinated adsorbent) is preferably 0.01 seconds or more and 6000 seconds or less. This makes it easier to suppress the generation of organic compounds other than the fluoroalkyne compound that originate from the fluoroalkyne compound during the dehydration treatment of the fluoroalkyne compound. The time is more preferably 0.1 seconds or more and 3000 seconds or less, and even more preferably 1 second or more and 1800 seconds or less.

[0035] Fluoroalkyne compounds Fluoroalkyne compounds are represented by formula 1. [ka] (In formula 1, R 1 and R 2 Each of these independently represents a hydrogen atom, a fluorine atom, or a fluoroalkyl group, R 1 and R 2 At least one of them represents the fluoroalkyl group.

[0036] In Formula 1 above, the number of carbon atoms in the fluoroalkyl group is preferably 1 or more and 4 or less. This makes it easier to suppress the generation of organic compounds other than the fluoroalkyne compound that originate from the fluoroalkyne compound during the dehydration treatment of the fluoroalkyne compound. In Formula 1 above, the number of carbon atoms in the fluoroalkyl group may be 1, 2, 3, or 4.

[0037] In Formula 1 above, the fluoroalkyl group is preferably a perfluoroalkyl group. This makes it easier to suppress the generation of organic compounds other than the fluoroalkyne compound that originate from the fluoroalkyne compound during the dehydration treatment of the fluoroalkyne compound.

[0038] In Formula 1 above, the fluoroalkyl group is preferably a CF3 group, a C2F5 group, a C3F7 group, or a C4F9 group. This makes it easier to suppress the generation of organic compounds other than the fluoroalkyne compound that originate from the fluoroalkyne compound during the dehydration treatment of the fluoroalkyne compound. The C3F7 group may be linear or branched. The C3F7 group may be -CF2CF2CF3 or -CF(CF3)2. The C4F9 group may be linear or branched. The C4F9 group may be -(CF2)3CF3, -CF2CF(CF3)2, -CF(CF3)CF2CF3, or -C(CF3)3.

[0039] In formula 1 above, R 1 and R 2 It is preferable that both are fluoroalkyl groups. This makes it easier to suppress the generation of organic compounds other than the fluoroalkyne compound that originate from the fluoroalkyne compound during the dehydration treatment of the fluoroalkyne compound.

[0040] Examples of fluoroalkyne 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, CF≡CCF3, CF≡CCF2CF3, CF≡CCF(CF3)2, CF≡CC(CF3)3, and the like.

[0041] In the water-containing fluoroalkyne compounds of this disclosure, the water content is preferably 0.001 vol ppm or more and 500 vol ppm or less. This makes it easier to suppress the generation of organic compounds other than the fluoroalkyne compound that originate from the fluoroalkyne compound during the dehydration treatment of the fluoroalkyne compound. The water content is more preferably 0.005 vol ppm or more and 400 vol ppm or less, and even more preferably 0.01 vol ppm or more and 300 vol ppm or less.

[0042] The water content mentioned above can be measured using a quartz crystal oscillating moisture meter.

[0043] The water-containing fluoroalkyne compounds disclosed herein may be prepared, for example, by synthesizing fluoroalkyne compounds using conventionally known methods, or by purchasing commercially available products.

[0044] ≪Fluorinated adsorbents≫ <Composition> The fluorine atom content in the fluorinated adsorbent of this disclosure is preferably 1 atm% or more. This makes it less likely for organic compounds other than the fluoroalkyne compound to be generated when a fluorinated adsorbent is used to dehydrate a fluoroalkyne compound containing water. The lower limit of the fluorine atom content in the fluorinated adsorbent is more preferably 1.5 atm% or more, and even more preferably 2 atm% or more. The upper limit of the fluorine atom content in the fluorinated adsorbent is not particularly limited, but for example, it is preferably 10 atm% or less, more preferably 8 atm% or less, and even more preferably 5 atm% or less. The fluorine atom content in the fluorinated adsorbent is preferably 1 atm% or more and 10 atm% or more, more preferably 1.5 atm% or more and 8 atm% or more, and even more preferably 2 atm% or more and 5 atm% or more. In this disclosure, "adsorbent" means one that adsorbs at least water.

[0045] The fluorine atom content in fluorinated adsorbents can be determined using X-ray photoelectron spectroscopy (XPS).

[0046] <Type> The fluorinated adsorbent may be at least one selected from the group consisting of, for example, fluorinated zeolite adsorbent, fluorinated activated carbon adsorbent, fluorinated alumina adsorbent, and fluorinated silica alumina. The fluorinated adsorbent is preferably a fluorinated zeolite adsorbent. In particular, fluorination of the aluminum oxide (Al2O3) contained in the zeolite adsorbent makes it easier to suppress the activity of the active sites of the zeolite adsorbent, thus making it easier to suppress the generation of organic compounds other than the fluoroalkyne compound that originate from the fluoroalkyne compound during the dehydration treatment of the fluoroalkyne compound. For the same reason, in the "step of treating the surface of the adsorbent with a fluorinating agent" described later, the adsorbent is preferably a zeolite adsorbent.

[0047] The fluorinated adsorbent being a fluorinated zeolite adsorbent can be identified by XPS or energy-dispersive X-ray spectroscopy (EDX). Similarly, in the "process of treating the surface of the adsorbent with a fluorinating agent" described later, the adsorbent being a zeolite adsorbent can also be identified.

[0048] The fluorinated zeolite adsorbent may contain cations. These cations are not particularly limited, but for example, H + Li + na + , K + Ca 2+ Mg 2+ Ba 2+ Examples include the following. From the viewpoint of suppressing the decomposition of the compound, the cation is Na + , K + Ca 2+ , and Mg 2+It is preferable that it be at least one selected from the group consisting of the following. The same applies when the adsorbent (in other words, the adsorbent before fluorination) is a zeolite adsorbent in the "step of treating the surface of the adsorbent with a fluorinating agent" described later.

[0049] The types of cations in fluorinated zeolite adsorbents can be identified by ion exchange chromatography. Furthermore, in the "step of treating the surface of the adsorbent with a fluorinating agent" described later, if the adsorbent is a zeolite adsorbent, the types of cations in the zeolite adsorbent can be identified in the same way as the methods for identifying the types of cations in "fluorinated zeolite adsorbents," except that the object of measurement is the "zeolite adsorbent" (in other words, the "zeolite adsorbent" before fluorination).

[0050] The zeolite constituting the fluorinated zeolite adsorbent may be an artificial zeolite or a natural zeolite, but is preferably an artificial zeolite such as a molecular sieve.

[0051] In the fluorinated zeolite adsorbent, the ratio N2 / N1, which is the number of silicon atoms to the number of aluminum atoms N1, is preferably 0.1 or more and 20 or less. This makes it easier to suppress the generation of organic compounds other than the fluoroalkyne compound that originate from the fluoroalkyne compound during the dehydration treatment of the fluoroalkyne compound. The ratio N2 / N1 is more preferably 1 or more and 10 or less, and even more preferably 2 or more and 6 or less.

[0052] In the fluorinated zeolite adsorbent, the above ratio N2 / N1 can be determined by XPS or EDX.

[0053] <Pore diameter> The fluorinated adsorbent has pores, and the pore diameter is preferably between 1 Å and 20 Å. This makes it easier to suppress the generation of organic compounds other than the fluoroalkyne compound that originate from the fluoroalkyne compound during the dehydration treatment of the fluoroalkyne compound. The pore diameter of the fluorinated adsorbent is more preferably between 2 Å and 15 Å, and even more preferably between 3 Å and 10 Å.

[0054] The above-mentioned pore diameter can be determined by using a specific surface area and pore distribution measuring device.

[0055] Fluorinated adsorbents may also be manufactured by performing the "step for obtaining a fluorinated adsorbent" described above as another step. The "step for obtaining a fluorinated adsorbent" may include the "step for treating the surface of the adsorbent with a fluorinating agent."

[0056] <Process of treating the surface of the adsorbent with a fluorinating agent> In the "step of treating the surface of the adsorbent with a fluorinating agent" described above, the reaction between the adsorbent and the fluorinating agent may be carried out in the liquid phase or in the gas phase. When carried out in the liquid phase, the reaction mode of the adsorbent and the fluorinating agent may be batch mode or flow mode (continuous mode), but batch mode is preferred. When carried out in the gas phase, the reaction mode of the adsorbent and the fluorinating agent may be batch mode or flow mode (continuous mode), but flow mode is preferred.

[0057] In the "reaction of adsorbent and fluorinating agent" described above, the amount of fluorinating agent per 100 parts by mass of adsorbent is preferably 0.01 parts by mass or more and 10,000 parts by mass or less. This makes it easier to produce fluorinated adsorbent, and thus makes it easier to suppress the generation of organic compounds other than the fluoroalkyne compound that originate from the fluoroalkyne compound during the dehydration treatment of the fluoroalkyne compound. The amount of fluorinating agent per 100 parts by mass of adsorbent is more preferably 0.1 parts by mass or more and 5,000 parts by mass or less, and even more preferably 1 part by mass or more and 3,000 parts by mass or less.

[0058] When carried out in the liquid phase, the temperature of the "reaction of adsorbent and fluorinating agent" is preferably between -50°C and 100°C. This makes it easier to generate fluorinated adsorbents, and thus makes it easier to suppress the generation of organic compounds other than the fluoroalkyne compound that originate from the fluoroalkyne compound during the dehydration treatment of the fluoroalkyne compound. The temperature is more preferably between -20°C and 75°C, and even more preferably between 0°C and 50°C.

[0059] When carried out in the gas phase, the temperature of the "reaction of adsorbent and fluorinating agent" is preferably 10°C to 500°C. This makes it easier to generate fluorinated adsorbents, and thus makes it easier to suppress the generation of organic compounds other than the fluoroalkyne compound that originate from the fluoroalkyne compound during the dehydration treatment of the fluoroalkyne compound. The temperature is more preferably 15°C to 450°C, and even more preferably 20°C to 400°C.

[0060] When carried out in the liquid phase, the pressure of the "reaction of adsorbent and fluorinating agent" described above is preferably between -80 kPaG and 3,000 kPaG in gauge pressure. This makes it easier to generate fluorinated adsorbents, and thus makes it easier to suppress the generation of organic compounds other than the fluoroalkyne compound that originate from the fluoroalkyne compound during the dehydration treatment of the fluoroalkyne compound. The pressure is more preferably between -50 kPaG and 2,500 kPaG in gauge pressure, and even more preferably between 0 kPaG and 2,000 kPaG.

[0061] When carried out in the gas phase, the pressure of the "reaction of adsorbent and fluorinating agent" described above is preferably 0 kPaG to 3,000 kPaG in gauge pressure. This makes it easier to generate fluorinated adsorbent, and thus makes it easier to suppress the generation of organic compounds other than the fluoroalkyne compound that originate from the fluoroalkyne compound during the dehydration treatment of the fluoroalkyne compound. The pressure is more preferably 5 kPaG to 2,500 kPaG in gauge pressure, and even more preferably 10 kPaG to 2,000 kPaG.

[0062] The reaction time between the adsorbent and the fluorinating agent (in other words, the contact time between the adsorbent and the fluorinating agent) is preferably 0.01 seconds or more and 6,000 seconds or less. This makes it easier to generate fluorinated adsorbent, and thus makes it easier to suppress the generation of organic compounds other than the fluoroalkyne compound that originate from the fluoroalkyne compound during the dehydration treatment of the fluoroalkyne compound. This time is more preferably 0.1 seconds or more and 3,000 seconds or less, and even more preferably 1 second or more and 1,800 seconds or less.

[0063] In the "step of treating the surface of the adsorbent with a fluorinating agent" described above, the fluorinating agent is at least one selected from the group consisting of hydrogen fluoride, fluorine, chlorodifluoromethane, dichlorofluoromethane, and fluoroalkyne compounds, and the fluoroalkyne compound is preferably represented by formula 2. [ka] (In formula 2, R 3 and R 4 Each of these independently represents a hydrogen atom, a fluorine atom, or a fluoroalkyl group, R 3 and R 4 At least one of them represents the fluoroalkyl group.

[0064] In Formula 2 above, the number of carbon atoms in the fluoroalkyl group is preferably 1 or more and 4 or less. This makes it easier to suppress the generation of organic compounds other than the fluoroalkyne compound that originate from the fluoroalkyne compound during the dehydration treatment of the fluoroalkyne compound. In Formula 2 above, the number of carbon atoms in the fluoroalkyl group may be 1, 2, 3, or 4.

[0065] In Formula 2 above, the fluoroalkyl group is preferably a perfluoroalkyl group. This makes it easier to suppress the generation of organic compounds other than the fluoroalkyne compound that originate from the fluoroalkyne compound during the dehydration treatment of the fluoroalkyne compound.

[0066] In Formula 2 above, the fluoroalkyl group is preferably a CF3 group, a C2F5 group, a C3F7 group, or a C4F9 group. This makes it easier to suppress the generation of organic compounds other than the fluoroalkyne compound that originate from the fluoroalkyne compound during the dehydration treatment of the fluoroalkyne compound. The C3F7 group may be linear or branched. The C3F7 group may be -CF2CF2CF3 or -CF(CF3)2. The C4F9 group may be linear or branched. The C4F9 group may be -(CF2)3CF3, -CF2CF(CF3)2, -CF(CF3)CF2CF3, or -C(CF3)3.

[0067] In equation 2 above, R 3 and R 4 It is preferable that both are fluoroalkyl groups. This makes it easier to suppress the generation of organic compounds other than the fluoroalkyne compound that originate from the fluoroalkyne compound during the dehydration treatment of the fluoroalkyne compound.

[0068] Examples of fluoroalkyne compounds represented by formula 2 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, CF≡CCF3, CF≡CCF2CF3, CF≡CCF(CF3)2, CF≡CC(CF3)3, and the like.

[0069] From the viewpoint of the production efficiency of the purified fluoroalkyne compound of Embodiment 1, it is preferable that the fluoroalkyne compound represented by Formula 2 is the same compound as the fluoroalkyne compound represented by Formula 1.

[0070] <Application> The purified fluoroalkyne compound obtained by the method for producing the purified fluoroalkyne compound 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.

[0071] [Embodiment 2: Method for producing a fluorinated adsorbent] A method for producing the fluorinated adsorbent according to this embodiment will be described. This embodiment is a method for producing a fluorinated adsorbent, comprising the step of treating the surface of the adsorbent with a fluorinating agent.

[0072] According to this disclosure, it is possible to provide a method for producing a fluorinated adsorbent that suppresses the generation of organic compounds other than the fluoroalkyne compound that originate from the fluoroalkyne compound during the dehydration treatment of the fluoroalkyne compound. The reason for this is presumed to be as described in Embodiments 1(a) and (b).

[0073] <Process of treating the surface of the adsorbent with a fluorinating agent> The "step of treating the surface of the adsorbent with a fluorinating agent" according to this embodiment is the same as the "step of treating the surface of the adsorbent with a fluorinating agent" according to Embodiment 1, so its explanation is omitted here.

[0074] <Application> The fluorinated adsorbent obtained by the method for producing the fluorinated adsorbent of this embodiment can be effectively used in applications such as dehydration of fluoroalkyne compounds containing water.

[0075] [Embodiment 3: Fluorinated Adsorbent] The fluorinated adsorbent according to this embodiment will be described. This embodiment is a fluorinated adsorbent for dehydrating fluoroalkyne compounds, The fluoroalkyne compound is represented by formula 1. [ka] (In formula 1, R 1 and R 2 Each of these independently represents a hydrogen atom, a fluorine atom, or a fluoroalkyl group, R 1 and R 2 At least one of them represents the fluoroalkyl group.

[0076] According to this disclosure, it is possible to provide a fluorinated adsorbent that can suppress the generation of organic compounds other than the fluoroalkyne compound that originate from the fluoroalkyne compound during the dehydration treatment of the fluoroalkyne compound. The reason for this is presumed to be as described in Embodiments 1(a) and (b).

[0077] ≪Fluorinated adsorbents≫ Since the fluorinated adsorbent according to this embodiment is the same as the fluorinated adsorbent according to Embodiment 1, its description will be omitted here.

[0078] Fluoroalkyne compounds Since the fluoroalkyne compound according to this embodiment is the same as the fluoroalkyne compound in Embodiment 1, its description is omitted here.

[0079] <Application> The fluorinated adsorbent in this embodiment is a fluorinated adsorbent for dehydrating fluoroalkyne compounds.

[0080] ≪Method for producing fluorinated adsorbents≫ The fluorinated adsorbent of this embodiment can be manufactured, for example, by the method for manufacturing a fluorinated adsorbent described in Embodiment 2.

[0081] 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]

[0082] This embodiment will be described in more detail by reference to examples. However, this embodiment is not limited by these examples.

[0083] <<Preparation of adsorbent>> The adsorbents for samples 1-8 and 101-104 were prepared as follows.

[0084] First, a SUS metal tube (1 / 2 inch in diameter, 30 cm in length) was filled with molecular sieves as a zeolite adsorbent, as described in Table 1 (pore size: as described in Table 1; ratio of silicon atoms N2 to aluminum atoms N1: as described in Table 1; cations contained in the zeolite adsorbent: as described in Table 1).

[0085] Next, the pressure inside the metal tube was reduced using a pump to the pressure shown in Table 1. Then, if a value greater than "0" was entered in the "Amount of fluorinating agent filled [g]" column of Table 1, the metal tube was filled with the amount of hexafluoro-2-butyne (fluorinating agent) shown in Table 1 at room temperature until the pressure inside the metal tube became atmospheric pressure, and the metal tube was left to stand for the time shown in Table 1 to fluorinate the molecular sieve (in other words, the zeolite adsorbent) shown in Table 1. The adsorbent for each sample was thus prepared.

[0086] ≪Evaluation of adsorbent properties≫ <Fluorine atom content in adsorbent> The fluorine atom content [atm%] in the adsorbent of each sample was measured using the method described in Embodiment 1. The results obtained are shown in the "Fluorine Atom Content [atm%]" column of Table 2.

[0087] <<Preparation of purified fluoroalkyne compounds>> In a metal tube filled with the adsorbent for each of the above samples, hexafluoro-2-butyne (a fluoroalkyne compound) with a water content of 52 vol ppm and a C4F7H content below the detection limit was passed through at a flow rate of 300 ccm for 30 minutes at room temperature to obtain purified fluoroalkyne compounds.

[0088] <Characterization of purified fluoroalkyne compounds> <Water> The water content of purified fluoroalkyne compounds was measured using a quartz crystal moisture meter. The results are shown in the "Water Content [volppm]" column of Table 2.

[0089] <c4f7h> The content of C4F7H (in other words, organic compounds other than the fluoroalkyne compound derived from the fluoroalkyne compound) in purified fluoroalkyne compounds was measured by gas chromatography. The results are shown in the "C4F7H content [volppm]" column of Table 2. "ND" (Not Detectable) means that the content was below the detection limit, specifically "less than 0.1 volppm".

[0090] If the C4F7H content in the purified fluoroalkyne compound is below the detection limit, it means that the generation of organic compounds other than the fluoroalkyne compound originating from the fluoroalkyne compound was suppressed during the dehydration treatment of the fluoroalkyne compound.

[0091] [Table 1]

[0092] [Table 2]

[0093] The methods for producing the purified fluoroalkyne compounds of Samples 1 to 8 correspond to the Examples. The methods for producing the purified fluoroalkyne compounds of Samples 101 to 104 correspond to the Comparative Examples. It was confirmed that the methods for producing the purified fluoroalkyne compounds of Samples 1 to 8 exhibit a particularly superior effect compared to the methods for producing the purified fluoroalkyne compounds of Samples 101 to 104, in that they enable the suppression of the generation of organic compounds other than the fluoroalkyne compound that originates from the fluoroalkyne compound during the dehydration treatment of the fluoroalkyne compound. Therefore, it was found that the methods for producing the purified fluoroalkyne compounds of Samples 1 to 8 enable the suppression of the generation of organic compounds other than the fluoroalkyne compound that originates from the fluoroalkyne compound during the dehydration treatment of the fluoroalkyne compound.

Claims

1. The process includes obtaining a purified fluoroalkyne compound by performing a dehydration treatment on a water-containing fluoroalkyne compound using a fluorinated adsorbent. The fluoroalkyne compound is represented by Formula 1, and the method for producing a purified fluoroalkyne compound. 【Chemistry 1】 (In formula 1, R １ and R ２ Each of these independently represents a hydrogen atom, a fluorine atom, or a fluoroalkyl group, R １ and R ２ At least one of them represents the fluoroalkyl group.

2. The method for producing a purified fluoroalkyne compound according to claim 1, wherein the fluorine atom content in the fluorinated adsorbent is 1 atm% or more.

3. The method for producing a purified fluoroalkyne compound according to claim 1 or claim 2, wherein the fluorinated adsorbent is a fluorinated zeolite adsorbent.

4. The fluoroalkyl group is CF ３ group, C ２ F ５ group, C ３ F ７ group, or C ４ F ９ group, and is a method for producing the purified fluoroalkyne compound according to claim 1 or claim 2.

5. A method for producing a fluorinated adsorbent, comprising a step of treating the surface of the adsorbent with a fluorinating agent.

6. The method for producing a fluorinated adsorbent according to claim 5, wherein the adsorbent is a zeolite adsorbent.

7. The fluorinating agent is at least one selected from the group consisting of hydrogen fluoride, fluorine, chlorodifluoromethane, dichlorofluoromethane, and fluoroalkyne compounds. The fluoroalkyne compound is represented by formula 2, and the method for producing a fluorinated adsorbent according to claim 5 or claim 6. 【Chemistry 2】 (In formula 2, R ３ and R ４ Each of these independently represents a hydrogen atom, a fluorine atom, or a fluoroalkyl group, R ３ and R ４ At least one of them represents the fluoroalkyl group.

8. The aforementioned fluoroalkyl group is CF ３ Group, C ２ F ５ Group, C ３ F ７ base, or C ４ F ９ The method for producing a fluorinated adsorbent according to claim 7.

9. A fluorinated adsorbent for dehydrating fluoroalkyne compounds, The fluoroalkyne compound is a fluorinated adsorbent represented by formula 1. 【Transformation 3】 (In formula 1, R １ and R ２ Each of these independently represents a hydrogen atom, a fluorine atom, or a fluoroalkyl group, R １ and R ２ At least one of them represents the fluoroalkyl group.

10. The fluorinated adsorbent according to claim 9, wherein the fluorine atom content in the fluorinated adsorbent is 1 atm% or more.

11. The fluorinated adsorbent according to claim 9 or claim 10, wherein the fluorinated adsorbent is a fluorinated zeolite adsorbent.

12. The aforementioned fluoroalkyl group is CF ３ Group, C ２ F ５ Group, C ３ F ７ base, or C ４ F ９ A fluorinated adsorbent according to claim 9 or claim 10, which is the base.

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