Method for producing perfluoroalkyne compound

Abstract

To provide a method which gives high reaction conversion, can give a perfluoroalkyne compound with high selectivity, and hardly produces a fluoroalkene compound as a byproduct, and also to provide a method for producing a perfluoroalkyne compound which can reduce deterioration of a catalyst.SOLUTION: A method comprises: setting a contact time of a catalyst and the perfluoroalkadiene compound to 30 seconds or less using a catalyst which comprises a catalyst selected from (a) a catalyst containing a prescribed element(s), (b) a catalyst containing at least two kinds of prescribed elements, (c) a fluorinated prescribed metal oxide(s) whose pore volume is in a prescribed range, (d) a metal oxide(s) fluorinated by a prescribed compound(s), and (e) a catalyst obtained by fluorinating a prescribed metal oxide(s) whose pore volume is in a prescribed range, or a prescribed element(s): or setting a moisture content in the reaction system in a prescribed range at at least one point from the start of the reaction to the end of the reaction.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present disclosure relates to a method for producing a perfluoroalkyne compound. [Background technology]

[0002] Perfluoroalkyne compounds are compounds that are expected to be used as dry etching gases for semiconductors, as well as various refrigerants, foaming agents, heat transfer media, etc., and are compounds that have one carbon-carbon triple bond. It is an object.

[0003] As a method for producing this perfluoroalkyne compound, the isomerization reaction of hexafluorobutadiene is known. For example, in Patent Document 1, hexafluorobutyne is obtained by isomerization of hexafluorobutadiene using halogenated alumina. In addition, in Patent Document 2, hexafluorobutyne is obtained from hexafluorocyclobutene using sodium fluoride or a mixture containing sodium fluoride as an isomerization reaction catalyst. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2012-001448 A [Patent Document 2] JP 2014-058488 A Summary of the Invention [Problem to be solved by the invention]

[0005] The present disclosure aims to provide a method for producing a perfluoroalkyne compound with high conversion and high selectivity, while suppressing the by-production of a fluoroalkene compound. Another aim of the present disclosure is to provide a method for producing a perfluoroalkyne compound, which can reduce catalyst deterioration. [Means for solving the problem]

[0006] The present disclosure encompasses the following configurations.

[0007] Item 1. A method for producing a perfluoroalkyne compound, comprising: A step of reacting a perfluoroalkadiene compound in the presence of a catalyst to obtain a perfluoroalkyne compound. The following (A) to (G): (A) the catalyst contains at least one catalyst selected from the group consisting of catalysts containing a transition metal element and catalysts containing at least two elements belonging to groups 3 to 14 of the periodic table; (B) The catalyst contains at least one element belonging to Groups 3 to 14 of the periodic table. death, the contact time between the catalyst and the perfluoroalkadiene compound is 30 seconds or less; (C) The catalyst comprises a fluorinated chromium oxide having a pore volume of 0.08 mL / g or more, a fluorinated alumina having a pore volume of 0.35 mL / g or more, and a fluorinated silica having a pore volume of 0.50 mL / g or more. At least one catalyst selected from the group consisting of silica and alumina, (D) the catalyst contains a fluorinated metal oxide having a pore volume of 0.35 mL / g or more; (E) The catalyst is a hydrofluorocarbon, a hydrochlorofluorocarbon, or a chlorofluorocarbon. At least one compound selected from the group consisting of fluorocarbons and a metal oxide. containing a metal oxide fluorinated by reacting (F) The catalyst is a chromium oxide having a pore volume of 0.10 mL / g or more, an alumina having a pore volume of 0.45 mL / g or more, At least one selected from the group consisting of lumina, and silica alumina having a pore volume of 0.50 mL / g or more. containing at least one metal oxide fluorinated catalyst, (G) Perfluoroalkadiene at least partially from the start of the reaction to the end of the reaction The mass of the compound is taken as the standard (100 mass%), and the water content in the reaction system is 30 mass ppm or less. reacting the perfluoroalkadiene compound; A manufacturing method that satisfies any one of the above.

[0008] Item 2. The perfluoroalkyne compound is represented by the general formula (1): CR 1 2R 2 -C≡C-CR 3 R 4 2(1) [In the formula, R 1 ~R 4 and are the same or different and represent a fluorine atom or a perfluoroalkyl group.

[0009] Item 3. The perfluoroalkadiene compound, General formula (2): CR 1 2=CR 2 -CR 3 =CR 4 2(2) [In the formula, R 1 ~R 4 and are the same or different and represent a fluorine atom or a perfluoroalkyl group.

[0010] Item 4. A catalyst which satisfies the above (A) or (B) and contains at least one transition metal element belonging to Groups 4 to 6 of the periodic table, and a catalyst which contains at least one transition metal element belonging to Groups 4 to 6 and Groups 13 to 14 of the periodic table. 4. The method according to any one of items 1 to 3, wherein the catalyst is at least one selected from the group consisting of catalysts containing at least two elements belonging to the group A, B, C and D.

[0011] Item 5. The production method according to any one of Items 1 to 4, which satisfies the above (A) or (B) and is at least one catalyst selected from the group consisting of an optionally fluorinated chromium oxide catalyst, an optionally fluorinated titanium oxide catalyst, an optionally fluorinated zirconia catalyst, and an optionally fluorinated silica-alumina catalyst.

[0012] Item 6. The above (D) is satisfied, and the metal constituting the fluorinated metal oxide is 4. The method according to any one of items 1 to 3, wherein at least one element belonging to groups 3 to 14 of the periodic table is included.

[0013] Item 7. The method according to any one of Items 1 to 3, wherein the condition (E) is satisfied and the metal oxide before being fluorinated has a pore volume of 0.45 mL / g or more.

[0014] Item 8. A metal that satisfies the above (E) and constitutes the metal oxide before being fluorinated. Item 8. The method according to item 1, 2, 3 or 7, wherein the compound contains at least one element belonging to groups 3 to 14 of the periodic table.

[0015] Item 9. The production method according to any one of Items 1 to 3, wherein the condition (G) is satisfied and the catalyst contains at least one element belonging to Groups 3 to 14 of the periodic table.

[0016] Item 10. The method according to any one of Items 1 to 9, wherein the reaction of the perfluoroalkadiene compound is carried out in a gas phase.

[0017] Item 11. The reaction of the perfluoroalkadiene compound is carried out at 170° C. or higher. The method for producing a product according to any one of claims 1 to 10.

[0018] Item 12. The method according to any one of Items 1 to 11, wherein a perfluorocycloalkene compound is also produced in addition to the perfluoroalkyne compound by the reaction of the perfluoroalkadiene compound.

[0019] Item 13. The perfluorocycloalkene compound, Formula (3):

[0020] [ka]

[0021] [In the formula, R 1 ~R 4 is the same as above.] Item 13. The method according to item 12, wherein the perfluorocycloalkene compound is represented by the formula:

[0022] Item 14. A method for producing a perfluoroalkyne compound, comprising: Item 14. A method for producing a perfluoroalkadiene compound, comprising the step of: obtaining the perfluoroalkadiene compound by using a perfluorocycloalkene compound produced as a by-product by the method for producing a perfluoroalkadiene compound according to item 12 or 13 as a substrate.

[0023] Item 15. The perfluoroalkyne compound is represented by the general formula (1): CR 1 2R 2 -C≡C-CR 3 R 4 2(1) [In the formula, R 1 ~R 4 and each may be the same or different and represent a fluorine atom or a perfluoroalkyl group.

[0024] Section 16. General formula (1): CR 1 2R 2 -C≡C-CR 3 R 4 2(1) [In the formula, R 1 ~R 4 and each may be the same or different and represent a fluorine atom or a perfluoroalkyl group. General formula (3):

[0025] [ka]

[0026] [In the formula, R 1 ~R 4 is the same as above.] A composition containing a perfluorocycloalkene compound represented by the formula: The total amount of the composition is taken as 100 mol %, and the perfluoroalkyne compound represented by the general formula (1) is The content of the compound is 40 to 99.999 mol %.

[0027] Item 17. The composition according to item 16, which is used as an etching gas or a building block for organic synthesis.

[0028] Item 18. A catalyst used to obtain a perfluoroalkyne compound by reacting a perfluoroalkadiene compound, comprising the following (C) to (D): (C) Fluorinated chromium oxide having a pore volume of 0.08 mL / g or more, and a pore volume of 0.35 mL / g or more Contains at least one selected from the group consisting of fluorinated alumina and fluorinated silica alumina having a pore volume of 0.50 mL / g or more; (D) containing a fluorinated metal oxide having a pore volume of 0.35 mL / g or more; A catalyst that satisfies any of the above.

[0029] Item 19. The above (D) is satisfied, and the metal constituting the fluorinated metal oxide is Item 19. The catalyst according to item 18, comprising at least one element belonging to groups 3 to 14 of the periodic table.

[0030] Item 20. A method for producing a catalyst used for reacting a perfluoroalkadiene compound to obtain a perfluoroalkyne compound, comprising the following (E) to (F): (E) Hydrofluorocarbons, hydrochlorofluorocarbons and chlorofluorocarbons At least one compound selected from the group consisting of carbon and a metal oxide is reacted with the compound. fluorinating the metal oxide by (F) chromium oxide having a pore volume of 0.10 mL / g or more, alumina having a pore volume of 0.45 mL / g or more, and At least one metal selected from the group consisting of silica alumina having a pore volume of 0.50 mL / g or more Fluorinating the oxide A manufacturing method comprising any one of the steps.

[0031] Item 21. The method according to item 20, wherein the condition (E) is satisfied and the pore volume of the metal oxide before fluorination is 0.45 mL / g or more.

[0032] Item 22. A gold oxide that satisfies the above (E) and is a metal oxide before being fluorinated. 22. The method according to item 20 or 21, wherein the group includes at least one element belonging to groups 3 to 14 of the periodic table. Effect of the Invention

[0033] According to the present disclosure, it is possible to provide a production method that is less likely to produce a fluoroalkene compound as a by-product, has a high reaction conversion rate, and can produce a perfluoroalkyne compound with high selectivity. In addition, according to the present disclosure, it is also possible to provide a production method for a perfluoroalkyne compound that can reduce catalyst deterioration. [Brief description of the drawings]

[0034] [Figure 1] 1 shows the relationship between reaction time and conversion when a fluorinated alumina catalyst is used. [Diagram 2] 1 shows the relationship between the pore volume before fluorination and the deterioration rate when a fluorinated alumina catalyst is used. [Diagram 3] 1 shows the relationship between the pore volume after fluorination and the deterioration rate when a fluorinated alumina catalyst is used. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0035] In this specification, "containing" is a concept that encompasses all of "comprise," "consist essentially of," and "consist only of." In addition, in this specification, when a numerical range is shown as "A to B," it means A or more and B or less.

[0036] 1. Catalyst and its manufacturing method The catalyst of the present disclosure is a catalyst used for reacting a perfluoroalkadiene compound to obtain a perfluoroalkyne compound, and has the following (C) to (D): (C) Fluorinated chromium oxide having a pore volume of 0.08 mL / g or more, and a pore volume of 0.35 mL / g or more Contains at least one selected from the group consisting of fluorinated alumina and fluorinated silica alumina having a pore volume of 0.50 mL / g or more; (D) containing a fluorinated metal oxide having a pore volume of 0.35 mL / g or more; Satisfy any of the following.

[0037] [1-1] Catalyst and its manufacturing method (Part 1) In the present disclosure, catalyst 1 (hereinafter, sometimes referred to as "isomerization catalyst 1") used to obtain a perfluoroalkyne compound by reacting (isomerization reaction) a perfluoroalkadiene compound contains at least one selected from the group consisting of fluorinated chromium oxide having a pore volume of 0.08 mL / g or more, fluorinated alumina having a pore volume of 0.35 mL / g or more, and fluorinated silica alumina having a pore volume of 0.50 mL / g or more. Satisfies requirement (C). The pore volume is the smallest among the conventionally used isomerization catalysts. It has not been optimized, and it is unclear what pore volume is being used. In the present disclosure, by using fluorinated metal oxides each having a specific pore volume, the conversion rate of the reaction can be increased, catalyst deterioration can be easily reduced, and catalyst deterioration can be suppressed even when the isomerization reaction is carried out for a long time. Therefore, when the catalyst of the present disclosure is adopted, the replacement frequency can be lengthened, which is economical.

[0038] The chromium oxide catalyst is not particularly limited, but when chromium oxide is expressed as CrO m it is preferably 1 < m < 3, more preferably 1.2 < m < 2, and even more preferably 1.3 < m < 1.8. Also, when chromium oxide is expressed as CrO m ·nH2O, it may be hydrated so that the value of n is 3 or less, particularly 1 to 1.5.

[0039] An example of a method for synthesizing a chromium oxide catalyst is shown below.

[0040] First, a precipitate of chromium hydroxide can be obtained by mixing an aqueous solution of a chromium salt (chromium nitrate, chromium chloride, chrome alum, chromium sulfate, etc.) and aqueous ammonia. The physical properties of chromium hydroxide can be controlled by the reaction rate of the precipitation reaction at this time. The reaction rate is preferably fast. The reaction rate depends on the reaction solution temperature, the method of mixing aqueous ammonia (mixing rate), the stirring state, etc.

[0041] After filtering and washing this precipitate, it can be dried. Drying can be carried out, for example, in air at 70 to 200 °C for 1 to 100 hours. The catalyst at this stage may be referred to as the state of chromium hydroxide. Next, this catalyst can be crushed. From the viewpoints of pellet strength, catalyst activity, etc., the crushed powder (for example, the particle size is 1000 μm or less, particularly 95% of the particle size product of 46 to 1000 μm) It is preferable to adjust the precipitation reaction rate so that the powder density is 0.6 to 1.1 g / ml, and preferably 0.6 to 1.0 g / ml. The specific surface area of ​​the powder (specific surface area by the BET method) is, for example, 100 m2 under degassing conditions of 200°C and 80 minutes. 2 / g or more is preferable, and 120m 2 The upper limit of the specific surface area is, for example, 220 m 2 / g.

[0042] This chromium hydroxide powder can be mixed with up to 3% by weight of graphite, if necessary, and formed into pellets using a tablet press. The size and strength of the pellets can be adjusted as appropriate.

[0043] The molded catalyst can be calcined in an inert atmosphere, for example, in a nitrogen stream, to form amorphous chromium oxide. The calcination temperature is preferably 360° C. or higher, and from the viewpoint of suppressing crystallization, a temperature of 380 to 460° C. is preferable. The calcination time can be, for example, 1 to 5 hours.

[0044] The specific surface area of ​​the calcined catalyst is, for example, 170 m from the viewpoint of catalytic activity. 2 / g or more is preferable. , 180m 2 / g or more is more preferable, and 200m 2 The upper limit of the specific surface area is usually 240 m 2 / g is preferable, and 220m 2 / g is more preferable.

[0045] Examples of the alumina catalyst include α-alumina and activated alumina. Lumina includes ρ-alumina, χ-alumina, κ-alumina, η-alumina, and pseudo-γ-alumina. Examples of suitable alumina include alumina, γ-alumina, σ-alumina, and θ-alumina.

[0046] In addition, a silica-alumina catalyst can also be used as the composite oxide. The silica-alumina catalyst is a composite oxide catalyst containing silica (SiO2) and alumina (Al2O3). For example, the silica content is 20 to 90 mass%, particularly 50 to 80 mass%, based on the total amount of alumina being 100 mass%. % by weight of catalyst can be used.

[0047] In the present disclosure, the above-mentioned metal oxide catalyst is fluorinated to obtain a fluorinated metal oxide catalyst. By fluorinating the metal oxide catalyst, the catalyst exhibits strong activity and is easy to reduce catalyst deterioration. By adjusting the pore volume, the catalyst deterioration can be suppressed even when the above-mentioned isomerization reaction is performed for a long period of time, so the catalyst is used as a fluorinated metal oxide catalyst. The method for fluorinating the metal oxide catalyst will be described later.

[0048] The catalyst of the present disclosure has a large pore volume because it reduces the deterioration of the catalyst and can suppress the deterioration of the catalyst even when the isomerization reaction is performed for a long period of time. Specifically, the pore volume of each metal oxide catalyst is 0.05 mL / g or more (particularly 0.075 to 1.5 mL / g) for fluorinated chromium oxide, 0.35 mL / g or more (particularly 0.40 to 2.0 mL / g) for fluorinated alumina, and 0.5 mL / g or more (particularly 0.5 mL / g to 1.0 mL / g) for fluorinated alumina. The pore volume of the silica alumina is 0.50 ml / g or more (especially 0.55 to 2.0 mL / g). If the pore volume is smaller than this range, the pores in which the active sites of the catalyst are present are covered with carbon, a by-product of the reaction, or the attached carbon reduces gas diffusion within the pores, causing a decrease in the activity of the catalyst, i.e., the catalyst is likely to deteriorate. Also, if the pore volume is too large, the manufacturing method of the catalyst becomes complicated, and the manufacturing cost increases.

[0049] The catalyst of the present disclosure has a large pore volume as described above. The pore volume can be adjusted by the degree of fluorination of the catalyst, that is, the content of fluorine atoms. Therefore, the total amount of the catalyst of the present disclosure is taken as 100 atomic %, and the content of fluorine atoms is preferably 5.0 to 50 atomic %, more preferably 10 to 25 atomic %.

[0050] As a method for fluorinating the metal oxide catalyst, for example, a metal oxide is reacted with a fluorinating agent. Specifically, for example, the fluorinating agent is passed through the metal oxide to fluorinate the metal oxide. The metal oxide in this case may be the metal oxide constituting the above-mentioned fluorinated metal oxide.

[0051] The metal oxide catalyst before fluorination is preferably large in pore volume because it can increase the pore volume of the metal oxide catalyst after fluorination, increase the conversion rate of the reaction, and easily reduce the deterioration of the catalyst, and it is easy to suppress the deterioration of the catalyst even if the above isomerization reaction is performed for a long time. Specifically, suitable pore volumes of each metal oxide catalyst before fluorination include, for example, chromium oxide is 0.05 mL / g or more (particularly 0.075 to 1.5 mL / g), alumina is 0.45 mL / g or more (particularly 0.50 to 2.5 mL / g), and silica alumina is 0.40 mL / g or more (particularly 0.50 to 2.0 mL / g). By setting the pore volume in this range, the active site of the catalyst is not easily covered by carbon, which is a by-product of the reaction, and the gas diffusion in the pores is not easily hindered by the attached carbon, so the activity of the catalyst is maintained, that is, the deterioration of the catalyst is easily suppressed, and the manufacturing method of the catalyst is also simple.

[0052] In this case, the fluorinating agent may be, for example, hydrofluorocarbon (R23: trifluorocarbon). Examples of fluorinating agents include hydrochlorofluorocarbons (R22: chlorodifluoromethane, R21: dichloromonofluoromethane), and chlorofluorocarbons (R13: chlorotrifluoromethane, R11: trichloromonofluoromethane). Compared with hydrogen fluoride, these fluorinating agents tend to increase the pore volume of the fluorinated metal oxide catalyst, making it easier to reduce catalyst deterioration and to inhibit catalyst deterioration when the above isomerization reaction is carried out for a long period of time. These fluorinating agents can be used alone or in combination of two or more.

[0053] The fluorination conditions are not particularly limited, but from the viewpoint of easily reducing catalyst deterioration and easily suppressing catalyst deterioration even when the above isomerization reaction is carried out for a long period of time, the temperature is preferably 50 to 600°C ( The temperature is preferably 100 to 500° C., the pressure is preferably 0 to 1000 kPa (particularly 0.1 to 500 kPa), and the time The time is preferably 0.1 to 24 hours (particularly 1 to 12 hours). In this way, it is preferable to adjust the content of fluorine atoms to be within the above range.

[0054] The perfluoroalkyne compound to be produced may be, for example, a compound represented by the general formula (1): CR 1 2R 2 -C≡C-CR 3 R 4 2(1) [In the formula, R 1 ~R 4 and are the same or different and each represents a fluorine atom or a perfluoroalkyl group.

[0055] In the general formula (1), R 1 ~R 4 The perfluoroalkyl group represented by the formula (I) is not particularly limited. Examples of the alkyl group include perfluoroalkyl groups having 1 to 6 carbon atoms (particularly 1 to 4 carbon atoms), such as a trifluoromethyl group and a pentafluoroethyl group.

[0056] In the general formula (1), R 1 ~R 4 The conversion rate of the reaction, the amount of the resulting perfluoroalkyl From the viewpoint of the yield and selectivity of the fluorine compound, it is preferable that each of R 1 ~R 4 may be the same or different.

[0057] From the above, the perfluoroalkyne compound represented by the general formula (1) to be produced is For example, CF3C≡CCF3, CF3C≡CCF2CF3, CF3C≡CCF(CF3)2, CF3C≡CC(CF3)3, CF3CF2C≡CCF2CF3, CF3CF2C≡CCF(CF3)2, CF3CF2C≡CC(CF3)3, (CF3)2CFC≡CCCF(CF3)2, (CF3)2CFC≡CC(CF3)3, (CF3)3CC≡CC(CF3)3, etc.

[0058] The perfluoroalkadiene compound as the substrate is, for example, a compound represented by the general formula (2): CR 1 2=CR 2 -CR 3 =CR 4 2(2) [In the formula, R 1 ~R 4 and are the same or different and each represents a fluorine atom or a perfluoroalkyl group.] is preferred.

[0059] In the general formula (2), R 1 ~R 4 The perfluoroalkyl group represented by the formula (I) is not particularly limited. Examples of the alkyl group include perfluoroalkyl groups having 1 to 6 carbon atoms (particularly 1 to 4 carbon atoms), such as a trifluoromethyl group and a pentafluoroethyl group.

[0060] In the general formula (2), R 1 ~R 4 The conversion rate of the reaction, the amount of the resulting perfluoroalkyl From the viewpoint of the yield and selectivity of the fluorine compound, it is preferable that each of R 1 ~R 4 may be the same or different.

[0061] As perfluoroalkadienes represented by the general formula (2) which satisfy the above conditions, , For example, 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)2, CF2=C(CF3)C(CF3)=CF2, etc. Lucadienes can be used alone or in combination of two or more.

[0062] The perfluoroalkadiene compounds described above can be publicly known or commercially available products, or can be synthesized according to the conventional method disclosed in JP-A-2001-192345.

[0063] [1-2] Catalyst and its manufacturing method (part 2) In the present disclosure, the catalyst 2 used to obtain a perfluoroalkyne compound by reacting (isomerizing) a perfluoroalkadiene compound (hereinafter, sometimes referred to as "isomerizing catalyst 2") contains a fluorinated metal oxide having a pore volume of 0.35 mL / g or more. This catalyst satisfies the above-mentioned requirement (D). Conventionally used isomerizing catalysts include In the case of the catalyst, the pore volume is not optimized, and it is unclear what kind of pore volume is used. In the present disclosure, by using a fluorinated metal oxide and increasing its pore volume to 0.35 mL / g or more, the conversion rate of the reaction is increased and deterioration of the catalyst is easily reduced, and deterioration of the catalyst can be suppressed even if the above isomerization reaction is carried out for a long period of time. Therefore, when the catalyst of the present disclosure is used, the replacement frequency can be increased, which is economical.

[0064] The catalyst of the present disclosure is not particularly limited, but from the viewpoint of increasing the conversion rate of the reaction, easily reducing catalyst deterioration, and easily suppressing catalyst deterioration even when the isomerization reaction is carried out over a long period of time, the metal constituting the fluorinated metal oxide is, for example, preferably at least one element belonging to Groups 3 to 14 of the periodic table, more preferably at least one element belonging to Groups 4 to 6 and Groups 13 to 14 of the periodic table, and more preferably chromium, titanium, silicon, etc. More preferably, the catalyst is at least one of the above-mentioned metals, aluminum, zirconium, etc. Only one type of metal element may be contained, or two or more types may be contained.

[0065] As such a catalyst of the present disclosure, from the viewpoints of having high activity in the isomerization reaction of a perfluoroalkadiene compound to a perfluoroalkyne compound, increasing the conversion rate of the reaction, and easily reducing catalyst deterioration, and making it easy to suppress catalyst deterioration even when the above-mentioned isomerization reaction is carried out over a long period of time, a fluorinated titanium oxide catalyst, a fluorinated alumina catalyst, a fluorinated silica-alumina catalyst, a fluorinated zirconia catalyst, etc. are particularly preferred.

[0066] The titanium oxide catalyst may contain titanium dioxide as the main component, and may contain one or more non-volatile substances such as other metal oxides, hydroxides, sulfates, nitrates, phosphates, sulfides, etc. In the titanium oxide catalyst, titanium dioxide is contained in an amount of 70 mass% or more. is preferred.

[0067] As the titanium dioxide, anatase type titanium dioxide is particularly preferable, and the specific surface area is preferably 5 to 100 m. 2 The catalyst preferably has a molecular weight of 0.1 to 0.5 ml / g and a pore volume of 0.2 to 0.4 ml / g. The catalyst is preferably molded into a spherical shape. Specifically, commercially available products under the trade names CS-200, CS-300, CS-950, etc. (manufactured by Sakai Chemical Industry Co., Ltd.) can be suitably used.

[0068] As the alumina catalyst and silica-alumina catalyst, those explained in the above [1-1] Catalyst and its production method (part 1) can be used.

[0069] The zirconia catalyst is not particularly limited as long as it contains zirconium oxide as the main component, and may contain one or more non-volatile substances such as other metal oxides, hydroxides, sulfates, nitrates, phosphates, sulfides, etc. The zirconia catalyst preferably contains 70 mass% or more of zirconia.

[0070] In the present disclosure, the above-mentioned metal oxide catalyst is fluorinated to obtain a fluorinated metal oxide catalyst. By fluorinating the metal oxide catalyst, the catalyst exhibits strong activity and is easy to reduce catalyst deterioration. By adjusting the pore volume, the catalyst deterioration can be suppressed even when the above-mentioned isomerization reaction is performed for a long period of time, so the catalyst is used as a fluorinated metal oxide catalyst. The method for fluorinating the metal oxide catalyst will be described later.

[0071] In the catalyst of the present disclosure, deterioration of the catalyst is easily reduced, and deterioration of the catalyst is easily suppressed even when the above-mentioned isomerization reaction is carried out for a long period of time, so it is preferable to increase the pore volume. Specifically, the pore volume of the metal oxide catalyst after fluorination is 0.35 mL / g or more, preferably 0.40 to 2.0 mL / g. The suitable pore volume of each metal oxide catalyst is, for example, The fluorinated alumina is 0.35mL / g or more (especially 0.40 to 2.0mL / g), and the fluorinated silica alumina is 0.35mL / g or more (especially 0.40 to 2.0mL / g). The pore volume is in this range. As a result, the active sites of the catalyst are less likely to be covered by carbon, a by-product of the reaction, and the gas diffusion within the pores is less likely to be hindered by the deposited carbon, which makes it easier to maintain the activity of the catalyst, i.e., to suppress catalyst deterioration, and also simplifies the method for producing the catalyst.

[0072] The degree of fluorination (i.e., the content of fluorine atoms), fluorination method, fluorinating agent, fluorination conditions, and the like of the catalyst of the present disclosure can be those described in the above [1-1] Catalyst and production method thereof (part 1).

[0073] The metal oxide catalyst before fluorination preferably has a large pore volume because it can increase the pore volume of the metal oxide catalyst after fluorination, increase the conversion rate of the reaction, and easily reduce catalyst deterioration. Even if the isomerization reaction is carried out over a long period of time, catalyst deterioration is easily suppressed. Specifically, the pore volume of the metal oxide catalyst before fluorination is preferably 0.45 mL / g or more, more preferably 0.50 to 2.5 mL / g. Note that, The preferred pore volume is, for example, 0.45 mL / g or more (particularly 0.50 to 2.5 mL / g) for alumina, and 0.50 to 2.5 mL / g for silica. Lumina is 0.40 mL / g or more (especially 0.50 to 2.0 mL / g). This makes it difficult for the active sites of the catalyst to be covered by carbon, a by-product of the reaction, and difficult for the attached carbon to inhibit gas diffusion within the pores, thereby maintaining the activity of the catalyst, i.e., making it easier to suppress catalyst deterioration, and also makes it easier to manufacture the catalyst.

[0074] The perfluoroalkyne compound to be produced and the perfluoroalkadiene compound as the substrate may be those explained in the above [1-1] Catalyst and Production Method thereof (Part 1).

[0075] 2. Catalyst manufacturing method The method for producing a catalyst according to the present disclosure is a method for producing a catalyst used for obtaining a perfluoroalkyne compound by reacting a perfluoroalkadiene compound, and includes the following steps (E) to (F): (E) Hydrofluorocarbons, hydrochlorofluorocarbons and chlorofluorocarbons At least one compound selected from the group consisting of carbon and a metal oxide is reacted with the compound. fluorinating the metal oxide by (F) chromium oxide having a pore volume of 0.10 mL / g or more, alumina having a pore volume of 0.45 mL / g or more, and At least one metal selected from the group consisting of silica alumina having a pore volume of 0.50 mL / g or more Fluorinating the oxide It has one of the following:

[0076] [2-1] Catalyst manufacturing method (part 3) In the present disclosure, a perfluoroalkadiene compound is reacted (isomerized) to form a perfluoro A method for producing a catalyst for obtaining a fluoroalkyne compound (hereinafter referred to as "isomerization reaction") The catalyst manufacturing method 3) is a process for producing hydrofluorocarbons and hydrochlorides. At least one compound selected from the group consisting of trifluorocarbons and a metal oxide. The method includes a step of fluorinating the metal oxide by reacting the metal oxide with the catalyst. This catalyst satisfies the above-mentioned requirement (E). As a catalyst for isomerization reaction that has been conventionally used, the pore volume is optimal. The catalyst has not been fluorinated, and it is unclear what kind of pore volume is used. In the present disclosure, the pore volume is adjusted to a predetermined range by performing fluorination with the above-mentioned specific compound, which increases the conversion rate of the reaction and makes it easy to reduce catalyst deterioration, and can suppress catalyst deterioration even when the above-mentioned isomerization reaction is performed for a long period of time. Therefore, when the catalyst of the present disclosure is used, the replacement frequency can be increased, which is economical.

[0077] The metal oxide is not particularly limited, but from the viewpoint of increasing the conversion rate of the reaction, easily reducing catalyst deterioration, and easily suppressing catalyst deterioration even when the isomerization reaction is carried out over a long period of time, it is preferable that the metal constituting the metal oxide is, for example, an element belonging to Groups 3 to 14 of the periodic table. At least one of the elements belonging to groups 4 to 6 and groups 13 to 14 of the periodic table is preferred. At least one of these is more preferable, and examples thereof include chromium, titanium, silicon, aluminum, zirconium, etc. At least one kind is more preferable. The metal oxide may contain only one kind of the above-mentioned metal elements, or may contain two or more kinds of them.

[0078] As such metal oxides, from the viewpoints of increasing the activity of the isomerization reaction from a perfluoroalkadiene compound to a perfluoroalkyne compound by fluorination as described above, increasing the conversion rate of the reaction, and easily reducing catalyst deterioration, and making it easy to suppress catalyst deterioration even when the isomerization reaction is carried out over a long period of time, chromium oxide catalysts, titanium oxide catalysts, alumina catalysts, silica-alumina catalysts, zirconia catalysts, and the like are particularly preferred.

[0079] As the chromium oxide catalyst, alumina catalyst and silica-alumina catalyst, those described in the above [1-1] Catalyst and its manufacturing method (part 1) can be used, and as the titanium oxide catalyst and zirconia catalyst, those described in the above [1-2] Catalyst and its manufacturing method (part 2) can be used.

[0080] The above-mentioned metal oxide catalyst before fluorination can have a larger pore volume after fluorination, which increases the conversion rate of the reaction and also reduces deterioration of the catalyst, and it is easy to suppress deterioration of the catalyst even when the isomerization reaction is carried out over a long period of time, so it is preferable that the pore volume is large. Specifically, the pore volume of the metal oxide catalyst before fluorination is preferably 0.45 mL / g or more, more preferably 0.50 to 2.5 mL / g. Note that, before fluorination, Suitable pore volumes for each of the metal oxide catalysts are, for example, 0.05 mL / g or more (particularly 0.075 to 1.5 mL / g) for chromium oxide, 0.45 mL / g or more (particularly 0.50 to 2.5 mL / g) for alumina, and 0.40 mL / g or more (particularly 0.50 to 2.0 mL / g) for silica alumina. By setting the pore volumes within these ranges, the active sites of the catalyst are less likely to be covered with carbon, which is a by-product of the reaction, and the gas diffusion within the pores is less likely to be hindered by the attached carbon, so that the activity of the catalyst is maintained, i.e., catalyst deterioration is easily suppressed, and the production method of the catalyst is also simple.

[0081] In the present disclosure, the above-mentioned metal oxide catalyst is fluorinated with a specific compound to obtain a fluorinated metal oxide catalyst. The fluorination makes the catalyst exhibit strong activity, and facilitates reduction in catalyst deterioration. By adjusting the pore volume, the catalyst deterioration can be suppressed even when the above-mentioned isomerization reaction is carried out for a long period of time, so the catalyst is used as a fluorinated metal oxide catalyst.

[0082] In the present disclosure, the method for fluorinating a metal oxide catalyst involves reacting the metal oxide with a fluorinating agent. Specifically, for example, a fluorinating agent is passed through the metal oxide to produce fluorine. It can be made into

[0083] In this disclosure, the fluorinating agent used in this case is a hydrofluorocarbon (R23: trifluoro At least one compound selected from the group consisting of fluoromethane (R32: difluoromethane, R41: monofluoromethane), hydrochlorofluorocarbons (R22: chlorodifluoromethane, R21: dichloromonofluoromethane), and chlorofluorocarbons (R13: chlorotrifluoromethane, R11: trichloromonofluoromethane) is used. In comparison with hydrogen fluoride, the pore volume of the fluorinated metal oxide catalyst is larger, which reduces the deterioration of the catalyst and suppresses the deterioration of the catalyst when the above isomerization reaction is carried out for a long period of time. These fluorinating agents can be used alone or in combination of two or more kinds.

[0084] The fluorination conditions are not particularly limited, but from the viewpoint of easily reducing catalyst deterioration and easily suppressing catalyst deterioration even when the above isomerization reaction is carried out for a long period of time, the temperature is preferably 50 to 600°C ( The temperature is preferably 100 to 500° C., the pressure is preferably 0 to 1000 kPa (particularly 0.1 to 500 kPa), and the time The time is preferably 0.1 to 24 hours (particularly, 1 to 12 hours).

[0085] The catalyst obtained in this manner has a large pore volume, which reduces the deterioration of the catalyst, and the deterioration of the catalyst can be suppressed even when the above-mentioned isomerization reaction is carried out for a long period of time. Specifically, the pore volume of the metal oxide catalyst after fluorination is preferably 0.35 mL / g or more, more preferably 0.40 to 2.0 mL / g. It is preferable that the pore volume of each metal oxide catalyst is, for example, 0.05 mL / g or more (particularly 0.075 to 1.5 mL / g) for fluorinated chromium oxide, 0.35 mL / g or more (particularly 0.40 to 2.0 mL / g) for fluorinated alumina, and 0.50 mL / g or more (particularly 0.55 to 2.0 mL / g) for fluorinated silica alumina. By setting the pore volume within this range, the active sites of the catalyst are less likely to be covered by carbon, which is a by-product of the reaction, and the gas diffusion in the pores is less likely to be hindered by the attached carbon, so that the activity of the catalyst is maintained, that is, the deterioration of the catalyst is easily suppressed, and the manufacturing method of the catalyst is also simple.

[0086] The catalyst obtained in this manner has a large pore volume, but the pore volume can also be adjusted by the degree of fluorination of the catalyst, that is, the content of fluorine atoms. Therefore, the total amount of the catalyst obtained after fluorination is taken as 100 atomic %, and the content of fluorine atoms is 5.0 to 50 atomic %. % is preferable, and 10 to 25 atomic % is more preferable.

[0087] The perfluoroalkyne compound to be produced and the perfluoroalkadiene compound as the substrate may be those explained in the above [1-1] Catalyst and Production Method thereof (Part 1).

[0088] [2-2] Catalyst manufacturing method (part 4) In the present disclosure, a method for producing a catalyst used for reacting (isomerizing) a perfluoroalkadiene compound to obtain a perfluoroalkyne compound (hereinafter, "method for producing the isomerizing reaction") is described. The catalyst manufacturing method 4) is a method in which the metal oxide before fluorination is The method includes a step of fluorinating at least one metal oxide selected from the group consisting of chromium oxide having a pore volume of 0.10 mL / g or more, alumina having a pore volume of 0.45 mL / g or more, and silica-alumina having a pore volume of 0.5 mL / g or more. This catalyst satisfies the above-mentioned requirement (F). The pore volume of the catalyst for the isomerization reaction is not optimized, and it is unclear what kind of pore volume is used. In the present disclosure, by fluorinating metal oxides each having a specific pore volume, the conversion rate of the reaction is increased, and the deterioration of the catalyst is easily reduced, so that the deterioration of the catalyst can be suppressed even if the above isomerization reaction is carried out for a long time. Therefore, when the catalyst of the present disclosure is adopted, the replacement frequency can be increased, which is economical.

[0089] As the chromium oxide catalyst, the alumina catalyst and the silica-alumina catalyst, those explained in the above [1-1] Catalyst and its production method (part 1) can be used.

[0090] The above-mentioned metal oxide catalyst before fluorination can increase the pore volume of the metal oxide catalyst after fluorination, increase the conversion rate of the reaction, reduce the deterioration of the catalyst, and suppress the deterioration of the catalyst even if the above-mentioned isomerization reaction is performed for a long time, so that a catalyst with a large pore volume is used. Specifically, the preferred pore volume of each metal oxide catalyst before fluorination is 0.05 mL / g or more (particularly 0.075 to 1.5 mL / g) for chromium oxide, 0.45 mL / g or more (particularly 0.50 to 2.5 mL / g) for alumina, and 0.40 mL / g or more (particularly 0.50 to 2.0 mL / g) for silica alumina. If the pore volume is smaller than this range, the pores in which the active sites of the catalyst exist are covered with carbon, which is a by-product of the reaction, or the gas diffusion in the pores is deteriorated due to the attached carbon, so that the activity of the catalyst decreases, that is, the catalyst is easily deteriorated. Moreover, if the pore volume is too large, the production method of the catalyst becomes complicated, resulting in increased production costs.

[0091] In the present disclosure, the above-mentioned metal oxide catalyst is fluorinated to obtain a fluorinated metal oxide catalyst. By fluorinating the metal oxide catalyst, the catalyst exhibits strong activity and is easy to reduce catalyst deterioration, and by adjusting the pore volume, the catalyst deterioration can be suppressed even when the above-mentioned isomerization reaction is carried out for a long period of time, so that the fluorinated metal oxide catalyst is used.

[0092] As for the fluorination method, fluorinating agent, and fluorination conditions, those explained in the above [1-1] Catalyst and production method thereof (part 1) can be used.

[0093] The catalyst obtained in this manner has a large pore volume, which reduces the deterioration of the catalyst, and the deterioration of the catalyst can be suppressed even if the above isomerization reaction is carried out for a long period of time. Specifically, the pore volume of each metal oxide catalyst is, for example, 0.05 mL / g or more (particularly, 0.075 to 1.5 mL / g) for fluorinated chromium oxide, 0.35 mL / g or more (particularly, 0.40 to 2.0 mL / g) for fluorinated alumina, The fluorinated silica alumina is preferably 0.50 ml / g or more (particularly 0.55 to 2.0 mL / g). By setting the volume within this range, the active sites of the catalyst are less likely to be covered by carbon, a by-product of the reaction, and the gas diffusion within the pores is less likely to be hindered by the deposited carbon, so that the activity of the catalyst is maintained, i.e., catalyst deterioration is easily suppressed, and the manufacturing method of the catalyst is also simple.

[0094] The catalyst obtained in this manner has a large pore volume, but the pore volume can also be adjusted by the degree of fluorination of the catalyst, that is, the content of fluorine atoms. Therefore, the total amount of the catalyst obtained after fluorination is taken as 100 atomic %, and the content of fluorine atoms is 5.0 to 50 atomic %. % is preferable, and 10 to 25 atomic % is more preferable.

[0095] The perfluoroalkyne compound to be produced and the perfluoroalkadiene compound as the substrate may be those explained in the above [1-1] Catalyst and Production Method thereof (Part 1).

[0096] 3. Method for producing perfluoroalkyne compounds The method for producing a perfluoroalkyne compound according to the present disclosure includes the steps of: A step of reacting a perfluoroalkadiene compound in the presence of a catalyst to obtain a perfluoroalkyne compound. The following (A) to (G): (A) the catalyst contains at least one catalyst selected from the group consisting of catalysts containing a transition metal element and catalysts containing at least two elements belonging to groups 3 to 14 of the periodic table; (B) The catalyst contains at least one element belonging to Groups 3 to 14 of the periodic table. death, the contact time between the catalyst and the perfluoroalkadiene compound represented by the general formula (2) is 30 seconds or less; (C) The catalyst comprises a fluorinated chromium oxide having a pore volume of 0.08 mL / g or more, a fluorinated alumina having a pore volume of 0.35 mL / g or more, and a fluorinated silica having a pore volume of 0.50 mL / g or more. At least one catalyst selected from the group consisting of silica and alumina, (D) the catalyst contains a fluorinated metal oxide having a pore volume of 0.35 mL / g or more; (E) The catalyst is a hydrofluorocarbon, a hydrochlorofluorocarbon, or a chlorofluorocarbon. At least one compound selected from the group consisting of fluorocarbons and a metal oxide. containing a metal oxide fluorinated by reacting (F) The catalyst is a chromium oxide having a pore volume of 0.10 mL / g or more, an alumina having a pore volume of 0.45 mL / g or more, A catalyst containing at least one metal oxide fluorinated catalyst selected from the group consisting of lumina and silica alumina having a pore volume of 0.50 mL / g or more. (G) Perfluoroalkadiene at least partially from the start of the reaction to the end of the reaction The mass of the compound is taken as the standard (100 mass%), and the water content in the reaction system is 30 mass ppm or less. reacting the perfluoroalkadiene compound; Satisfy any of the following.

[0097] As the perfluoroalkyne compound and the perfluoroalkadiene compound, those explained in the above [1-1] Catalyst and its production method (part 1) can be used.

[0098] [3-1] Method for producing perfluoroalkyne compounds (part 1) A first method for producing a perfluoroalkyne compound according to the present disclosure includes the steps of: A step of reacting a perfluoroalkadiene compound in the presence of a catalyst to obtain a perfluoroalkyne compound. The catalyst is a catalyst containing a transition metal element and an element belonging to groups 3 to 14 of the periodic table. and at least one catalyst selected from the group consisting of at least two of the following: This production method satisfies the above-mentioned requirement (A).

[0099] Conventionally, methods for producing perfluoroalkyne compounds have used catalysts that do not contain transition metals and contain only one Group 13 element, such as halogenated alumina or sodium fluoride. There are only examples using catalysts containing alkali metals. According to the present disclosure, by using a catalyst containing a transition metal element not previously known or a catalyst containing at least two elements belonging to Groups 3 to 14 of the periodic table, the conversion rate of the reaction is high, and perfluoroalkyne compounds can be obtained in high yield and high selectivity, and the range of options for synthesizing perfluoroalkyne compounds can be expanded. In this way, by using a catalyst containing a highly active transition metal element or a catalyst containing at least two elements belonging to Groups 3 to 14 of the periodic table whose activity increases when made into a composite oxide, the conversion rate of the reaction is high, and perfluorocycloalkene compounds can be obtained with high selectivity. Moreover, according to the present disclosure, unlike the conventional methods, fluoroalkene compounds are less likely to be by-produced as described below.

[0100] In the present disclosure, a catalyst containing a transition metal element or a catalyst containing a group 3 element of the periodic table is used as a catalyst for the isomerization reaction. A catalyst containing at least two elements belonging to Group 14 of the present invention is used. From the viewpoint of achieving a particularly high conversion rate in the reaction and obtaining a perfluoroalkyne compound in a high yield and with a high selectivity, a catalyst containing at least one transition metal element belonging to Groups 4 to 6 of the periodic table, or a catalyst containing at least one transition metal element belonging to Groups 4 to 6 and Groups 13 to 14 of the periodic table is preferred, although it is not particularly limited thereto. Catalysts containing at least two of the above are preferred, and catalysts containing chromium, titanium, zirconium, etc. and catalysts containing silicon and aluminum are more preferred.

[0101] As a catalyst for such an isomerization reaction, there is a catalyst having high activity in the isomerization reaction from perfluoroalkadiene compounds to perfluoroalkyne compounds, and depending on the reaction conditions, there is a catalyst having high activity in the isomerization reaction from perfluoroalkadiene compounds to perfluoroalkyne compounds. Like the quinone compounds, they have high activity in the production reaction of perfluorocycloalkene compounds which are expected to be used not only as dry etching gases for semiconductors, but also as various refrigerants, foaming agents, heat transfer media, etc., and therefore preferred are chromium oxide catalysts which may be fluorinated (chromium oxide catalyst or fluorinated chromium oxide catalyst), titanium oxide catalysts which may be fluorinated (titanium oxide catalyst or fluorinated titanium oxide catalyst), zirconia catalysts which may be fluorinated (zirconia catalyst or fluorinated zirconia catalyst), silica-alumina catalysts which may be fluorinated (silica-alumina catalyst or fluorinated silica-alumina catalyst), etc.

[0102] As the chromium oxide catalyst and silica alumina catalyst, those described in the above [1-1] Catalyst and its manufacturing method (part 1) can be used, and as the titanium oxide catalyst and zirconia catalyst, those described in the above [1-2] Catalyst and its manufacturing method (part 2) can be used.

[0103] In addition, when the catalyst is fluorinated, the degree of fluorination (content of fluorine atoms), the fluorination method, the fluorinating agent, and the fluorination conditions can be those described in the above [1-1] Catalyst and production method thereof (part 1).

[0104] These isomerization catalysts can be used alone or in combination of two or more. It is also possible.

[0105] The amount of catalyst used in the above-mentioned isomerization reaction can be a catalytic amount and is not particularly limited, but from the viewpoint of particularly high conversion rate of the reaction and obtaining a perfluoroalkyne compound in a higher yield and with a higher selectivity, 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, more preferably 0.5 to 150 g·sec. / cc. When a plurality of catalysts for the isomerization reaction are used, it is preferable to adjust the total amount to be within the above range. The above W / F is particularly important in the case of a gas-phase reaction, and is particularly important in determining the amount of catalyst. However, even when a liquid phase reaction is employed, the amount of the fluoride used can be a catalytic amount and can be appropriately adjusted.

[0106] In the production method of the present disclosure, when the reaction of a perfluoroalkadiene compound is carried out, in addition to the perfluoroalkadiene compound as the substrate and the catalyst for the isomerization reaction, metallic nickel (particularly metallic nickel beads), activated carbon, or the like can also be used for the purpose of heat transfer or diluting the catalyst concentration, so that the W / F is 0.1 to 200 g sec. / cc, particularly 0.5 to 150 g sec. / cc.

[0107] The production method of the present disclosure (particularly the reaction of the perfluoroalkadiene compound) can be carried out in a liquid phase, but is preferably carried out in a gas phase, particularly in a gas phase continuous flow system using a fixed bed reactor. This can further simplify the device, operation, etc. compared to the case of carrying out in a liquid phase, and can obtain the perfluoroalkyne compound in a higher yield and higher selectivity compared to the case of carrying out in a batch system.

[0108] In the production method of the present disclosure, the reaction of the perfluoroalkadiene compound is preferably carried out under heating. Specifically, it is preferable to heat the system after the perfluoroalkadiene compound as the substrate and the catalyst for the isomerization reaction are charged into the system. The heating temperature at this time is preferably 170° C. or higher (particularly 170 to 400° C.), more preferably 180 to 280° C., from the viewpoint of particularly high conversion rate of the reaction and of being able to obtain the perfluoroalkyne compound in a higher yield and with a higher selectivity. stomach.

[0109] In the production method of the present disclosure, the contact time (reaction time) between the catalyst and the perfluoroalkadiene compound is not particularly limited. From the viewpoint of achieving a particularly high conversion rate in the reaction and obtaining the perfluoroalkyne compound in a higher yield and with a higher selectivity, the contact time is preferably 1 to 100 seconds, more preferably 2 to 30 seconds. This is more preferable.

[0110] In the production method of the present disclosure, the atmosphere in which the perfluoroalkadiene compound is reacted is not particularly limited, and for example, the reaction atmosphere is preferably an inert gas atmosphere (such as a nitrogen gas atmosphere or an argon gas atmosphere).

[0111] In the production method of the present disclosure, not only a perfluorocycloalkene compound but also a perfluorocycloalkene compound can be produced. The perfluorocycloalkene compound is represented by the general formula (3):

[0112] [ka]

[0113] [In the formula, R 1 ~R 4 is the same as above.] The perfluorocycloalkene compound is represented by the following formula: The perfluorocycloalkene compound will be described in detail later.

[0114] Therefore, after the reaction is completed, if necessary, purification treatment can be carried out in accordance with a conventional method to obtain a perfluoroalkyne compound.

[0115] In addition, the perfluorocycloalkene compound by-produced by the production method of the present disclosure may be purified according to a conventional method as necessary, and then the perfluorocycloalkene compound may be used as a substrate to obtain a perfluoroalkyne compound. The method and conditions for this purpose may be those described in Patent Document 2 (JP Patent Publication 2014-058488 A). Preferred specific examples may also be used.

[0116] Specifically, a perfluorocycloalkene compound can be used as a substrate and isomerized using an isomerization catalyst to obtain a perfluoroalkyne compound. This process can be carried out in a gas phase, particularly in a gas phase continuous flow system using a fixed bed reactor, but can also be carried out by a batch reaction.

[0117] As a catalyst for the isomerization reaction, it is preferable to use sodium fluoride, which has low hygroscopicity and is therefore easy to handle in the air, and which can provide high activity and high selectivity. When sodium fluoride itself is used as a catalyst, it may be in powder form, but pellet form is preferable for gas-phase continuous flow reactions. It is also possible to use sodium fluoride supported on a carrier such as alumina, porous aluminum fluoride, activated carbon, silica, or zeolite. It is also possible to use sodium fluoride mixed with other components.

[0118] The temperature of the isomerization reaction is usually preferably from 200 to 800°C, more preferably from 400 to 600°C.

[0119] Not only the perfluoroalkyne compounds obtained as described above, but also the perfluorocycloalkene compounds can be effectively used in a variety of applications, such as etching gases for forming cutting-edge fine structures in semiconductors, liquid crystals, etc., as well as building blocks for organic synthesis. The synthetic building blocks will be described in detail later.

[0120] [3-2] Method for producing perfluoroalkyne compounds (part 2) A second method for producing a perfluoroalkyne compound according to the present disclosure includes the steps of: A step of reacting a perfluoroalkadiene compound in the presence of a catalyst to obtain a perfluoroalkyne compound. the catalyst contains at least one element belonging to groups 3 to 14 of the periodic table, and the contact time between the catalyst and the perfluoroalkadiene compound is 30 seconds or less. This production method satisfies the above-mentioned requirement (B).

[0121] Conventionally, methods for producing perfluoroalkyne compounds have used catalysts that do not contain transition metals and contain only one Group 13 element, such as halogenated alumina or sodium fluoride. There are examples of catalysts containing alkali metals, but when taking the example of a catalyst that does not contain a transition metal and contains only one Group 13 element, there are only examples of long reaction times of 32 seconds or more. According to the present disclosure, by using a catalyst containing at least one element belonging to Groups 3 to 14 of the periodic table and setting the reaction time to 30 seconds or less, the conversion rate of the reaction is high, and perfluoroalkyne compounds can be obtained in high yield and high selectivity, thereby widening the range of options when synthesizing perfluoroalkyne compounds. According to this method, the reaction time is short, so the reaction can proceed economically. Moreover, according to the present disclosure, unlike conventional methods, fluoroalkene compounds are less likely to be by-produced, as described below.

[0122] In the present disclosure, a small amount of elements belonging to groups 3 to 14 of the periodic table is used as a catalyst for isomerization reaction. The catalyst used is at least one of the following: From the viewpoint of being able to obtain a perfluoroalkyne compound in a higher yield and with a higher selectivity, a catalyst containing a transition metal element or a catalyst containing a small amount of an element belonging to Groups 3 to 14 of the periodic table is particularly preferred. A catalyst containing at least two of the transition metal elements belonging to groups 4 to 6 of the periodic table is preferred. and a catalyst containing at least one of the elements belonging to groups 4 to 6 and groups 13 to 14 of the periodic table. More preferred are catalysts containing at least two of these metals, such as chromium, titanium, zirconium, etc., and catalysts containing ketone, etc. Catalysts containing iodine and aluminum are more preferred.

[0123] As a catalyst for such an isomerization reaction, chromium oxide catalysts which may be fluorinated (chromium oxide catalyst or fluorinated chromium oxide catalyst), titanium oxide catalysts which may be fluorinated (titanium oxide catalyst or fluorinated titanium oxide catalyst), zirconia catalysts which may be fluorinated (zirconia catalyst or fluorinated zirconia catalyst), silica alumina catalysts which may be fluorinated (silica alumina catalyst or fluorinated silica alumina catalyst), etc. are preferred, since they have high activity in the isomerization reaction from perfluoroalkadiene compounds to perfluoroalkyne compounds and, depending on the reaction conditions, have high activity in the production reaction of perfluorocycloalkene compounds which are expected to be used as dry etching gases for semiconductors as well as various refrigerants, foaming agents, heat transfer media, etc., similar to perfluoroalkyne compounds. In this embodiment, fluorinated catalysts containing one element belonging to Group 13 of the periodic table are preferably used. Alternatively, an alumina catalyst may be used.

[0124] As the chromium oxide catalyst, alumina catalyst and silica-alumina catalyst, those described in the above [1-1] Catalyst and its manufacturing method (part 1) can be used, and as the titanium oxide catalyst and zirconia catalyst, those described in the above [1-2] Catalyst and its manufacturing method (part 2) can be used.

[0125] These isomerization catalysts can be used alone or in combination of two or more. It is also possible.

[0126] In addition, when the catalyst is fluorinated, the degree of fluorination (content of fluorine atoms), the fluorination method, the fluorinating agent, and the fluorination conditions can be those described in the above [1-1] Catalyst and production method thereof (part 1).

[0127] The amount of the catalyst used in the above isomerization reaction can be that explained in the above [3-1] Production method for a perfluoroalkyne compound (part 1).

[0128] In the production method of the present disclosure, when the reaction of a perfluoroalkadiene compound is carried out, in addition to the perfluoroalkadiene compound as the substrate and the catalyst for the isomerization reaction, metallic nickel (particularly metallic nickel beads), activated carbon, or the like can also be used for the purpose of heat transfer or diluting the catalyst concentration, so that the W / F is 0.1 to 200 g sec. / cc, particularly 0.5 to 150 g sec. / cc.

[0129] The production method of the present disclosure (particularly the reaction of the perfluoroalkadiene compound) can be carried out in a liquid phase, but is preferably carried out in a gas phase, particularly in a gas phase continuous flow system using a fixed bed reactor. This can further simplify the device, operation, etc. compared to the case of carrying out in a liquid phase, and can obtain the perfluoroalkyne compound in a higher yield and higher selectivity compared to the case of carrying out in a batch system.

[0130] In the production method of the present disclosure, the reaction temperature and reaction atmosphere in the reaction of the perfluoroalkadiene compound may be those described in the above [3-1] Production method of a perfluoroalkyne compound (part 1).

[0131] In the manufacturing method of the present disclosure, the contact time (reaction time) between the catalyst and the perfluoroalkadiene compound is 30 seconds or less, preferably 25 seconds or less. If the contact time (reaction time) exceeds 30 seconds, the yield of the perfluoroalkyne compound decreases. The lower limit of the contact time (reaction time) is not particularly limited, but is usually 1 second.

[0132] In the production method of the present disclosure, not only a perfluorocycloalkene compound but also a perfluorocycloalkene compound can be produced. The perfluorocycloalkene compound is represented by the general formula (3):

[0133] [ka]

[0134] [In the formula, R 1 ~R 4 is the same as above.] The perfluorocycloalkene compound is represented by the following formula: The perfluorocycloalkene compound will be described in detail later.

[0135] Therefore, after the reaction is completed, if necessary, purification treatment can be carried out in accordance with a conventional method to obtain a perfluoroalkyne compound.

[0136] In addition, the perfluorocycloalkene compound produced as a by-product in the production method of the present disclosure may be purified according to a conventional method as necessary, and then the perfluorocycloalkene compound may be used as a by-product in the production method of the present disclosure. It is also possible to obtain a perfluoroalkyne compound by using a kenyl compound as a substrate. The method and conditions for this can be those described in the above [3-1] Method for producing a perfluoroalkyne compound (part 1).

[0137] Not only the perfluoroalkyne compounds obtained as described above, but also the perfluorocycloalkene compounds can be effectively used for various applications such as etching gases for forming cutting-edge fine structures in semiconductors, liquid crystals, etc., building blocks for organic synthesis, etc. Details of building blocks for organic synthesis will be described later.

[0138] [3-3] Method for producing perfluoroalkyne compounds (part 3) A third method for producing a perfluoroalkyne compound according to the present disclosure comprises: A step of reacting a perfluoroalkadiene compound in the presence of a catalyst to obtain a perfluoroalkyne compound. The following (C) to (F): (C) The catalyst comprises a fluorinated chromium oxide having a pore volume of 0.08 mL / g or more, a fluorinated alumina having a pore volume of 0.35 mL / g or more, and a fluorinated silica having a pore volume of 0.50 mL / g or more. At least one catalyst selected from the group consisting of silica and alumina, (D) the catalyst contains a fluorinated metal oxide having a pore volume of 0.35 mL / g or more; (E) The catalyst is a hydrofluorocarbon, a hydrochlorofluorocarbon, or a chlorofluorocarbon. At least one compound selected from the group consisting of fluorocarbons and a metal oxide. containing a metal oxide fluorinated by reacting (F) The catalyst is a chromium oxide having a pore volume of 0.10 mL / g or more, an alumina having a pore volume of 0.45 mL / g or more, A catalyst containing at least one metal oxide fluorinated catalyst selected from the group consisting of lumina and silica alumina having a pore volume of 0.50 mL / g or more. Satisfy any of the following.

[0139] Requirement (C) is the present invention described in the above [1-1] Catalyst and its manufacturing method (part 1). Requirement (D) means using the catalyst 2 for the isomerization reaction of the present disclosure described in the above [1-2] Catalyst and its production method (part 2). Requirement (E) means that in the above [2-1] catalyst production method (part 3), It is intended to use a catalyst obtained by the above-described method for producing a catalyst for isomerization reaction according to the present disclosure. The requirement (F) is as described in the above [2-2] Catalyst Production Method (Part 4). This means using a catalyst obtained by the method for producing an isomerization catalyst according to the present disclosure. The catalysts of the present disclosure may be used alone or in combination of two or more. Cut.

[0140] In the present disclosure, by using the catalyst of the present disclosure as described above, the conversion rate of the reaction is increased, and the deterioration of the catalyst is easily reduced, and the deterioration of the catalyst can be suppressed even when the isomerization reaction is carried out for a long period of time. Therefore, the replacement frequency of the catalyst of the present disclosure can be increased, which is an economical method.

[0141] The amount of the catalyst of the present disclosure used as described above can be a catalytic amount and is not particularly limited. However, from the viewpoint of particularly high conversion rate of the reaction, easy reduction in catalyst deterioration, and easy suppression of catalyst deterioration even when the isomerization reaction is carried out over a long period of time, for example, the catalyst weight ratio (W / F) to the perfluoroalkadiene compound supply rate per hour is preferably 0.1 to 200 g·sec. / cc. In addition, when a plurality of catalysts according to the present disclosure are used, It is preferable to adjust the total amount to be within the above range. However, even when a liquid phase reaction is adopted, the amount of catalyst used may be a catalytic amount and may be appropriately adjusted.

[0142] In the production method of the present disclosure, in addition to the perfluoroalkadiene compound as the substrate and the catalyst of the present disclosure, the isomerization reaction can also use metallic nickel (particularly metallic nickel beads), activated carbon, or the like for the purpose of heat transfer or diluting the catalyst concentration, so that the W / F is 0.1 to 200 g sec. / cc, particularly 0.5 to 150 g sec. / cc.

[0143] In the production method of the present disclosure, isomerization reaction can be carried out in liquid phase, but is preferably carried out in gas phase, particularly in gas phase continuous flow using fixed bed reactor.Therefore, compared with the case of carrying out in liquid phase, the device, operation, etc. can be further simplified, and compared with the case of carrying out in batch mode, perfluoroalkyne compound can be obtained in higher yield and higher selectivity, and further, deterioration of catalyst can be easily reduced, and deterioration of catalyst can be easily suppressed even if the above isomerization reaction is carried out for a long time.

[0144] In the production method of the present disclosure, the isomerization reaction is preferably carried out by heating. Specifically, it is preferable to heat the system after the perfluoroalkadiene compound as the substrate and the catalyst of the present disclosure are charged into the system. The heating temperature at this time is preferably 170°C or higher (particularly 170 to 400°C), more preferably 180 to 280°C, from the viewpoints of particularly high conversion rate of the reaction, easy reduction in catalyst deterioration, and easy suppression of catalyst deterioration even when the isomerization reaction is carried out for a long period of time.

[0145] In the production method of the present disclosure, the reaction time in the isomerization reaction is not particularly limited, but since the present disclosure is likely to reduce catalyst deterioration and suppresses deterioration even when the above-mentioned isomerization reaction is carried out over a long period of time, it is suitable for a long-term reaction, preferably 10 to 200 hours, and more preferably 20 to 100 hours.

[0146] In the production method of the present disclosure, the atmosphere in the isomerization reaction is not particularly limited, and for example, the reaction atmosphere is preferably an inert gas atmosphere (nitrogen gas atmosphere, argon gas atmosphere, etc.).

[0147] After completion of the reaction, purification treatment can be carried out according to a conventional method, if necessary, to obtain a perfluoroalkyne compound.

[0148] The perfluoroalkyne compounds obtained as described above can be effectively used for various applications such as etching gases for forming cutting-edge fine structures in semiconductors, liquid crystals, etc., as well as building blocks for organic synthesis, etc. Details of building blocks for organic synthesis will be described later.

[0149] [3-4] Method for producing perfluoroalkyne compounds (part 4) A fourth method for producing a perfluoroalkyne compound according to the present disclosure includes the steps of: A step of reacting a perfluoroalkadiene compound in the presence of a catalyst to obtain a perfluoroalkyne compound. and at least part of the time from the start of the reaction to the end of the reaction, the water content in the reaction system is 30 ppm by mass or less, based on the mass of the perfluoroalkadiene compound (100% by mass). Then, the perfluoroalkadiene compound is reacted.

[0150] As a method for producing a perfluoroalkyne compound, a method of isomerizing a perfluoroalkadiene compound by reacting it in the presence of a catalyst is known, but no method capable of reducing catalyst deterioration is known. According to the present disclosure, by making the amount of water in the reaction system 30 mass ppm or less based on the mass of the perfluoroalkadiene compound (100 mass%) at least in a part from the start of the reaction to the end of the reaction, catalyst deterioration is reduced and the conversion rate of the reaction is maintained. In this case, it is possible to suppress the deterioration of the catalyst even if the above-mentioned isomerization reaction is carried out for a long time. In this case, the deterioration rate of the catalyst also varies depending on the catalyst weight ratio (W / F) to the perfluoroalkadiene compound supply rate per hour. In other words, by increasing the W / F, the deterioration rate of the catalyst is reduced. By slowing down the supply rate of the fluoroalkadiene compound, it is possible to further suppress the deterioration of the catalyst, and therefore, when the production method of the present disclosure is adopted, the catalyst can be replaced more frequently, making it an economical method.

[0151] Although the details will be described later, according to the present disclosure, the amount of water present in the reaction system is kept low. Therefore, it is possible to effectively prevent the active points of the catalyst from being crushed by water and thus deteriorating. In other words, regardless of the type of catalyst used, it is possible to prevent the active points of the catalyst from being crushed by water, and it is possible to effectively reduce the deterioration of the catalyst. The catalyst for the isomerization reaction is not particularly limited, but from the viewpoint that reducing the amount of water in the reaction system makes it easier to reduce catalyst deterioration and makes it easier to suppress deterioration even when the isomerization reaction is carried out over a long period of time, for example, a catalyst containing at least one element belonging to Groups 3 to 14 of the periodic table is preferable, and a catalyst containing at least one element belonging to Groups 4 to 6 and Groups 13 to 14 of the periodic table is preferable. More preferably, the catalyst contains at least one of chromium, titanium, silicon, aluminum, etc. The catalyst may contain only one type of the above-mentioned metal elements, or may contain two or more types of them.

[0152] As the catalyst for such an isomerization reaction, from the viewpoints of high activity in the isomerization reaction from a perfluoroalkadiene compound to a perfluoroalkyne compound, and of easily reducing catalyst deterioration by reducing the amount of water in the reaction system, and thus easily suppressing deterioration even when the isomerization reaction is carried out over a long period of time, particularly preferred are chromium oxide catalysts which may be fluorinated (chromium oxide catalyst or fluorinated chromium oxide catalyst), titanium oxide catalysts which may be fluorinated (titanium oxide catalyst or fluorinated titanium oxide catalyst), alumina catalysts which may be fluorinated (alumina catalyst or fluorinated alumina catalyst), silica-alumina catalysts which may be fluorinated (silica-alumina catalyst or fluorinated silica-alumina catalyst), and the like.

[0153] As the chromium oxide catalyst, alumina catalyst and silica-alumina catalyst, those described in the above [1-1] Catalyst and its manufacturing method (part 1) can be used, and as the titanium oxide catalyst and zirconia catalyst, those described in the above [1-2] Catalyst and its manufacturing method (part 2) can be used.

[0154] These isomerization catalysts can be used alone or in combination of two or more. It is also possible.

[0155] In addition, when the catalyst is fluorinated, the degree of fluorination (content of fluorine atoms), the fluorination method, the fluorinating agent, and the fluorination conditions can be those described in the above [1-1] Catalyst and production method thereof (part 1).

[0156] The amount of the catalyst used in the above isomerization reaction can be that explained in the above [3-1] Production method for a perfluoroalkyne compound (part 1).

[0157] In the production method according to the present disclosure, in addition to the perfluoroalkadiene compound as the substrate and the catalyst for the isomerization reaction (the reaction of a perfluoroalkadiene compound), metallic nickel (particularly metallic nickel beads), activated carbon, or the like can also be used for the purpose of improving heat transfer or diluting the catalyst concentration, so that the W / F is 0.1 to 200 g sec. / cc, and particularly 0.5 to 150 g sec. / cc.

[0158] In the production method of the present disclosure, the isomerization reaction (reaction of a perfluoroalkadiene compound) is carried out under conditions where the amount of water in the reaction system is 30 ppm by mass or less, preferably 20 ppm by mass or less, based on the mass of the perfluoroalkadiene compound (100 mass%), at least partly from the start of the reaction to the end of the reaction. The lower limit of the water amount can be 1 ppb by mass. In the present disclosure, the amount of water in the reaction system can be determined, for example, by filling the reaction atmosphere with an inert gas, as described below. The moisture content can be adjusted by supplying a perfluoroalkadiene compound having a specific moisture content while maintaining the atmosphere.

[0159] In this disclosure, the amount of water in the reaction system is 30 mass ppm or less as described above. The amount of water in the reaction system may be 30 mass ppm or less at the start of the reaction, or may be increased during the reaction. The amount of water in the reaction system may be 30 ppm by mass or less, or the amount of water in the reaction system at the end of the reaction may be 30 ppm by mass or less. In other words, the amount of water in the reaction system is 30 ppm by mass or less at least partly (at least at any timing) from the start of the reaction to the end of the reaction. Among these, from the viewpoint of further suppressing catalyst deterioration, it is preferable that the amount of water in the reaction system is 30 ppm by mass or less (particularly 20 ppm by mass or less) at least at the start of the reaction, and it is particularly preferable that the amount of water in the reaction system is 30 ppm by mass or less (particularly 20 ppm by mass or less) from the start of the reaction to the end of the reaction.

[0160] In the production method of the present disclosure, the reaction atmosphere in the isomerization reaction (reaction of a perfluoroalkadiene compound) is not particularly limited as long as the amount of water in the reaction system is within the above-mentioned range, and for example, an inert gas atmosphere (nitrogen gas atmosphere, argon gas atmosphere, etc.) is preferable. When the reaction atmosphere is an inert gas atmosphere, the amount of water in the reaction system is 30 mass ppm or less, and In other words, the water content of the perfluoroalkadiene compound, which is the substrate, is 30 mass ppm or less. In other words, the reaction atmosphere is an inert gas atmosphere. In this case, the production method of the present disclosure includes the step of producing a perfluorinated cellulose having a water content of 30 mass ppm or less in the presence of a catalyst. In other words, it is a method for obtaining a perfluoroalkyne compound by reacting a perfluoroalkadiene compound with a catalyst. In this case, the water content of the perfluoroalkyne compound may be 30 mass ppm or less immediately before the reaction, that is, immediately before contacting with the catalyst, or the water content of the perfluoroalkyne compound in the reaction system during the reaction may be 30 mass ppm or less. The water content of the fluoroalkyne compound may be 30 ppm by mass or less, and at the end of the reaction, The water content of the fluoroalkyne compound may be 30 mass ppm or less. The water content of the perfluoroalkyne compound may be 30 ppm by mass or less at least during at least a part (at least any timing) from the start of the reaction to the end of the reaction. It is preferable that the water content of the perfluoroalkyne compound is 30 mass ppm or less. It is particularly preferable that the water content of the perfluoroalkyne compound is 30 ppm by mass or less from the start to the end of the reaction.

[0161] In the manufacturing method of the present disclosure, isomerization reaction (reaction of perfluoroalkadiene compound) can be carried out in liquid phase, but it is preferable to carry out in gas phase, particularly in gas phase continuous flow type using fixed bed reactor.Therefore, compared with the case of carrying out in liquid phase, the device, operation, etc. can be further simplified, and compared with the case of carrying out in batch type, perfluoroalkyne compound can be obtained in higher yield and higher selectivity, and further, by reducing the amount of water in the reaction system, catalyst deterioration can be easily reduced, and deterioration can be easily suppressed even if the above isomerization reaction is carried out for a long time.

[0162] In the production method of the present disclosure, the reaction temperature in the reaction of the perfluoroalkadiene compound may be the same as that explained in the above [3-1] Production method of a perfluoroalkyne compound (part 1).

[0163] In the production method of the present disclosure, there is no particular restriction on the reaction time in the isomerization reaction (reaction of a perfluoroalkadiene compound); however, the present disclosure is suitable for long-term reactions because it reduces the amount of water in the reaction system, which makes it easy to reduce catalyst deterioration and suppresses deterioration even when the isomerization reaction is carried out over a long period of time. It is preferably 10 to 200 hours, and more preferably 20 to 100 hours.

[0164] After the reaction is completed, purification is carried out according to a conventional method as necessary to obtain the perfluoroalkyne. The compound can be obtained.

[0165] The perfluoroalkyne compounds obtained as described above can be effectively used for various applications such as etching gases for forming cutting-edge fine structures in semiconductors, liquid crystals, etc., as well as building blocks for organic synthesis, etc. Details of building blocks for organic synthesis will be described later.

[0166] 4. Perfluorocycloalkene composition As described above, a perfluoroalkyne compound can be obtained, but when the manufacturing method described in the above [3-1] Manufacturing method for perfluoroalkyne compound (part 1) or [3-2] Manufacturing method for perfluoroalkyne compound (part 2) is adopted, the perfluoroalkyne compound may be obtained in the form of a perfluoroalkyne composition containing a perfluoroalkyne compound and a perfluorocycloalkene compound as described above. Note that, when the manufacturing method described in the above [3-3] Manufacturing method for perfluoroalkyne compound (part 3) or [3-4] Manufacturing method for perfluoroalkyne compound (part 4) is adopted, the selectivity of the obtained perfluoroalkyne compound is extremely high, and the content of other additional compounds in the product can be extremely reduced.

[0167] When the perfluoroalkyne compound is obtained in the form of a perfluoroalkyne composition, the perfluoroalkyne compound is represented by the general formula (1): CR 1 2R 2 -C≡C-CR 3 R 4 2(1) [In the formula, R 1 ~R 4 is the same as above.] The perfluorocycloalkene compound is preferably a perfluoroalkyne represented by the general formula (3):

[0168] [ka]

[0169] [In the formula, R 1 ~R 4 is the same as above.] In the perfluoroalkyne composition of the present disclosure, the perfluoroalkyne compound may be used alone or in combination with two or more kinds. The above can also be used in combination.

[0170] Examples of the perfluorocycloalkene compound include:

[0171] [ka]

[0172] The perfluorocycloalkene compound may be used alone or in combination of two or more kinds. The above can also be used in combination.

[0173] In the perfluoroalkyne composition of the present disclosure, the content of the perfluoroalkyne compound is 40 to 99.999 mol % based on the total amount of the perfluoroalkyne composition of the present disclosure being 100 mol %. The content of the perfluorocycloalkene compound is preferably 0.001 to 60 mol%, more preferably 0.002 to 50 mol%, and even more preferably 0.003 to 40 mol%, based on the total amount of the perfluoroalkyne composition of the present disclosure being 100 mol%.

[0174] In addition, according to the production method of the present disclosure, in addition to the above-mentioned perfluoroalkyne compounds and perfluorocycloalkene compounds, General formula (4A): CR 1 2=CR 2 -CFR 3 -CFR 4 2(4A) [In the formula, R 1 ~R 4 is the same as above.] and perfluoroalkene compounds represented by the formula: General formula (4B): CFR 1 2-CR 2 =CH-CFR 4 2(4B) [In the formula, R 1 ~R 4 is the same as above.] A fluoroalkene compound represented by the formula: According to the production method of the present disclosure, the fluoroalkene compound represented by general formula (4B) is hardly produced as a by-product.

[0175] Therefore, the perfluoroalkyne composition of the present disclosure may also contain a perfluoroalkene compound represented by general formula (4A) or a fluoroalkene compound represented by general formula (4B). When the perfluoroalkyne composition of the present disclosure contains a perfluoroalkene compound represented by general formula (4A), the content thereof is preferably 0.0005 to 0.5 mol %, and more preferably 0.001 to 0.3 mol %, based on the total amount of the perfluoroalkyne composition of the present disclosure being 100 mol %. When the perfluoroalkyne composition of the present disclosure contains a fluoroalkene compound represented by general formula (4B), the fluoroalkene compound represented by general formula (4B) is unlikely to be by-produced according to the production method of the present disclosure, and therefore the content thereof is preferably 0 to 0.3 mol %, and more preferably 0.01 to 0.28 mol %, relative to the total amount of the perfluoroalkyne composition of the present disclosure being 100 mol %.

[0176] According to the production method of the present disclosure, even if a perfluoroalkyne composition is obtained, the perfluoroalkyne compound can be obtained in a particularly high yield and with a high selectivity as described above, and therefore, components other than the perfluoroalkyne compound in the perfluoroalkyne composition can be obtained. Since it is possible to reduce the amount of the perfluoroalkyne compound, the purification effort required to obtain the perfluoroalkyne compound can be reduced.

[0177] The perfluoroalkyne composition of the present disclosure can be effectively used for a variety of applications, such as an etching gas for forming cutting-edge fine structures in semiconductors, liquid crystals, etc., as well as building blocks for organic synthesis, just like the above-mentioned perfluoroalkyne compound alone. The building block for organic synthesis means a substance that can be a precursor of a compound having a highly reactive skeleton. For example, when the perfluorocycloalkene composition of the present disclosure is reacted with a fluorine-containing organosilicon compound such as CF3Si(CH3)3, it is possible to introduce a fluoroalkyl group such as a CF3 group and convert it into a substance that can be a cleaning agent or a fluorine-containing pharmaceutical intermediate.

[0178] Although the embodiment of the present disclosure has been described above, various changes in form and details are possible without departing from the spirit and scope of the claims. EXAMPLES

[0179] The following examples will clarify the features of the present disclosure, but the present disclosure is not limited to these examples.

[0180] [Example 1: Requirement (A) or (B)] In the following Example 1, the following catalyst was used: Chromia catalyst: Cr2O3 Fluorinated chromia catalyst (1): Cr2O3 was fluorinated by passing hydrogen fluoride through it at atmospheric pressure at 100-460℃ for 3-4 hours. Titania catalyst: TiO2 Fluorinated titania catalyst: Circulate hydrogen fluoride at atmospheric pressure and at room temperature to 300°C for 3 to 4 hours. TiO2 was fluorinated with Fluorinated zirconia catalyst: Circulate hydrogen fluoride at atmospheric pressure at room temperature to 400°C for 3 to 4 hours. ZrO2 was fluorinated with Silica-alumina catalyst: SiO2 / Al2O3=80 / 10~60 / 20 (mass ratio).

[0181] Example 1-1: Fluorinated chromia catalyst; W / F = 30.0 g·sec. / cc; 200°C; 23.1 seconds The catalyst, fluorinated chromia catalyst (1) (chromia fluorinated with hydrogen fluoride), was packed into a metal tubular reactor. The reaction tube was heated to 200°C and hexafluorobutadiene (CF2CF=CFCF2) was fed into the reaction tube so that the W / F was 30.0 g·sec. / cc, resulting in a continuous gas-phase flow. The reaction was carried out for 23.1 seconds in the normal manner. After 1 hour had elapsed since the end of the reaction, the gas flowing out of the reaction tube was Chromatographic analysis revealed that the conversion was 100 mol%, and the selectivity of each component was 99.7 mol% for 1,1,1,4,4,4-hexafluoro-2-butyne (CF3C≡CCF3), 0.162 mol% for 1,2,3,3,4,4-hexafluoro-1-cyclobutene (c-C4F6), 0.0356 mol% for 1,1,2,3,3,4,4,4-octafluoro-1-butene (CF2=CFCF2CF3) (total amount of E and Z isomers), and 0.189 mol% for 1,1,1,2,4,4,4-heptafluoro-1-butene (CF2=CFCF2CF3). Trifluoro-2-butene (CF3CF=CHCF3) was 0.0947 mol% (total amount of E and Z isomers), and other by-products The total product was 0.0182 mol %.

[0182] Example 1-2: Fluorinated chromia catalyst; W / F = 30.0 g·sec. / cc; 250°C; 23.1 seconds The reaction was carried out in the same manner as in Example 1-1, except that the heating temperature was 250° C. and the reaction was carried out for 23.1 seconds. After 1 hour had elapsed since the end of the reaction, the gas flowing out of the reaction tube was analyzed by gas chromatography. The conversion rate was 100 mol%, and the selectivity of each component was 97.2 mol% for 1,1,1,4,4,4-hexafluoro-2-butyne (CF3C≡CCF3), 97.2 mol% for 1,2,3,3,4,4-hexafluoro-1-cyclobutyne, and 97.2 mol% for 1,2,3,3,4,4-hexafluoro-1-cyclobutyne. Butene (c-C4F6) 2.47 mol%, 1,1,2,3,3,4,4,4-octafluoro-1-butene (CF2=CFCF2CF3) 0.0871 mol% (total amount of E- and Z-isomers), 1,1,1,2,4,4,4-heptafluoro-2-butene (CF3CF=CHCF3) 0.262 mol% (total amount of E- and Z-isomers), and other by-products total 0.0194 mol%. It was.

[0183] Example 1-3: Fluorinated chromia catalyst; W / F = 90.0 g·sec. / cc; 200°C; 69.3 seconds The reaction was carried out in the same manner as in Example 1-1, except that the W / F was set to 90.0 g·sec. / cc and the reaction was carried out for 69.3 seconds. After 1 hour had passed since the end of the reaction, the gas flowing out of the reaction tube was analyzed by gas chromatography. The conversion rate was 100 mol% and the selectivity of each component was 99.7 mol% for 1,1,1,4,4,4-hexafluoro-2-butyne (CF3C≡CCF3), 99.7 mol% for 1,2,3,3,4,4-hexafluoro-1-cyano, and 99.7 mol% for 1,2,3,3,4,4-hexafluoro-1-cyano. Clobutene (c-C4F6) was 0.118 mol%, 1,1,2,3,3,4,4,4-octafluoro-1-butene (CF2=CFCF2CF3) was 0.0254 mol% (total amount of E and Z isomers), and 1,1,1,2,4,4,4-heptafluoro-2-butene was 0. The amount of tetracycline (CF3CF=CHCF3) was 0.0911 mol% (total amount of E-isomer and Z-isomer), and the amount of other by-products was 0.0162 mol% in total.

[0184] Example 1-4: Fluorinated titania catalyst; W / F = 30.0 g·sec. / cc; 200°C; 32.5 seconds The reaction was carried out in the same manner as in Example 1-1, except that a fluorinated titania catalyst (titania fluorinated with hydrogen fluoride) was used as the catalyst and the reaction was carried out for 32 seconds. After filtration, the outflow gas from the reaction tube was analyzed by gas chromatography, and the conversion was found to be 99.0 mol%. The selectivity of each component was 99.3 mol% for 1,1,1,4,4,4-hexafluoro-2-butyne (CF3C≡CCF3), 0.354 mol% for 1,2,3,3,4,4-hexafluoro-1-cyclobutene (c-C4F6), 0.0595 mol% (total amount of E-isomer and Z-isomer) for 1,1,1,2,4,4,4-heptafluoro-2-butene (CF3CF=CHCF3) and 0.0341 mol% (total amount of E-isomer and Z-isomer) for other by-products.

[0185] Example 1-5: Fluorinated titania catalyst; W / F = 30.0 g·sec. / cc; 250°C; 32.5 seconds The reaction was carried out in the same manner as in Example 1-1, except that a fluorinated titania catalyst (titania fluorinated with hydrogen fluoride) was used as the catalyst, the heating temperature was set to 250° C., and the reaction was carried out for 32.5 seconds. After one hour had passed since the end of the reaction, the gas flowing out of the reaction tube was analyzed by gas chromatography. Analysis revealed that the conversion rate was 99.9 mol%, and the selectivity of each component was 1,1,1,4,4,4-hexafluorophenyl. 23.7 mol% fluoro-2-butyne (CF3C≡CCF3), 1,2,3,3,4,4-hexafluoro-1-cyclobutyne The content of the product was 76.0 mol% of c-C4F6, 0.00110 mol% of 1,1,2,3,3,4,4,4-octafluoro-1-butene (CF2=CFCF2CF3) (total amount of E- and Z-isomers), 0.00421 mol% of 1,1,1,2,4,4,4-heptafluoro-2-butene (CF3CF=CHCF3) (total amount of E- and Z-isomers), and a total of 0.295 mol% of other by-products.

[0186] Example 1-6: Fluorinated titania catalyst; W / F = 30.0 g·sec. / cc; 300°C; 32.5 seconds The reaction was carried out in the same manner as in Example 1-1, except that a fluorinated titania catalyst (titania fluorinated with hydrogen fluoride) was used as the catalyst, the heating temperature was set to 300° C., and the reaction was carried out for 32.5 seconds. After one hour had passed since the end of the reaction, the gas flowing out of the reaction tube was analyzed by gas chromatography. Analysis revealed that the conversion was 100 mol%, and the selectivity of each component was 44.5 mol% for 1,1,1,4,4,4-hexafluoro-2-butyne (CF3C≡CCF3), 55.1 mol% for 1,2,3,3,4,4-hexafluoro-1-cyclobutene (c-C4F6), 0.00601 mol% (total amount of E- and Z-isomers) for 1,1,2,3,3,4,4,4-octafluoro-1-butene (CF2=CFCF2CF3), 0.00200 mol% (total amount of E- and Z-isomers) for 1,1,1,2,4,4,4-heptafluoro-2-butene (CF3CF=CHCF3), and 0.392 mol% in total for other by-products.

[0187] Example 1-7: Fluorinated zirconia catalyst; W / F = 30.0 g·sec. / cc; 250°C; 14.9 seconds The reaction was carried out in the same manner as in Example 1-1, except that a fluorinated zirconia catalyst (zirconia fluorinated with hydrogen fluoride) was used as the catalyst, the heating temperature was set to 250° C., and the reaction was carried out for 14.9 seconds. After 1 hour had elapsed since the end of the reaction, the gas flowing out of the reaction tube was analyzed by gas chromatography. The conversion rate was 70.1 mol%, and the selectivity of each component was 1,2,3,3,4,4-hex. 4.18 mol% of 1,1,1,4,4,4-hexafluoro-2-cyclobutene (c-C4F6) was The content of fluorine (CF3C≡CCF3) was 94.1 mol%, 1,1,2,3,3,4,4,4-octafluoro-1-butene (CF2=CFCF2CF3) was 0.00100 mol% (total amount of E- and Z-isomers), 1,1,1,2,4,4,4-heptafluoro-2-butene (CF3CF=CHCF3) was 0.198 mol% (total amount of E- and Z-isomers), and other by-products were 0.0760 in total. The molar percentage was

[0188] Example 1-8: Fluorinated zirconia catalyst; W / F = 30.0 g·sec. / cc; 350°C; 14.9 seconds The reaction was carried out in the same manner as in Example 1-1, except that a fluorinated zirconia catalyst (zirconia fluorinated with hydrogen fluoride) was used as the catalyst, the heating temperature was set to 350° C., and the reaction was carried out for 14.9 seconds. After 1 hour had elapsed since the end of the reaction, the gas flowing out of the reaction tube was analyzed by gas chromatography. The conversion rate was 99.5 mol % and the selectivity of each component was 1,1,1,4,4,4-hex. The content of trifluoro-2-butyne (CF3C≡CCF3) was 2.68 mol%, 1,2,3,3,4,4-hexafluoro-1-cyclobutene (c-C4F6) was 96.3 mol%, 1,1,2,3,3,4,4,4-octafluoro-1-butene (CF2=CFCF2CF3) was 0.0127 mol% (total amount of E- and Z-isomers), 1,1,1,2,4,4,4-heptafluoro-2-butene (CF3CF=CHCF3) was 0.118 mol% (total amount of E- and Z-isomers), and other by-products were a total of 0.274 mol%.

[0189] Example 1-9: Fluorinated zirconia catalyst; W / F = 15.0 g·sec. / cc; 350°C; 7.5 seconds The experiment was carried out using a fluorinated zirconia catalyst (zirconia fluorinated with hydrogen fluoride) as the catalyst, setting the heating temperature at 350°C, setting the W / F at 15.0 g·sec. / cc, and carrying out the reaction for 7.5 seconds. The reaction was carried out in the same manner as in Example 1-1. After 1 hour had elapsed since the end of the reaction, the gas flowing out of the reaction tube was The conversion rate was 99.1 mol%. The selectivity was 3.71 mol% for 1,1,1,4,4,4-hexafluoro-2-butyne (CF3C≡CCF3), 95.3 mol% for 1,2,3,3,4,4-hexafluoro-1-cyclobutene (c-C4F6), and 1,1,2,3,3,4,4,4-octafluoro 0.0163 mol% of fluoro-1-butene (CF2 = CFCF2CF3) (total amount of E and Z isomers), 0.0851 mol% of 1,1,1,2,4,4,4-heptafluoro-2-butene (CF3CF = CHCF3) (total amount of E and Z isomers), The total amount of other by-products was 0.246 mol %.

[0190] The results of Examples 1-1 to 1-9 are shown in Table 1.

[0191] [Table 1]

[0192] Example 1-10: Fluorinated chromia catalyst; W / F = 15.0 g·sec. / cc; 200°C; 16.2 seconds The reaction was carried out in the same manner as in Example 1-1, except that the W / F was set to 15.0 g·sec. / cc and the reaction was carried out for 16.2 seconds. After 1 hour had passed since the end of the reaction, the gas flowing out of the reaction tube was analyzed by gas chromatography. The conversion was 100 mol% and the selectivity of each component was 99.8 mol% for 1,1,1,4,4,4-hexafluoro-2-butyne (CF3C≡CCF3), 0.0991 mol% for 1,2,3,3,4,4-hexafluoro-1-cyclobutene (c-C4F6), below the detection limit (ND; total amount of E and Z isomers) for 1,1,2,3,3,4,4,4-octafluoro-1-butene (CF2=CFCF2CF3), 0.0850 mol% for 1,1,1,2,4,4,4-heptafluoro-2-butene (CF3CF=CHCF3) (total amount of E and Z isomers), and 0.0850 mol% for other by-products. The total was 0.0159 mol %.

[0193] Example 1-11: Chromia catalyst; W / F = 30.0 g·sec. / cc; 20°C; 25.1 seconds The reaction was carried out in the same manner as in Example 1-1, except that a chromia catalyst was used as the catalyst, the heating temperature was set to 20° C., and the reaction was carried out for 25.1 seconds. After 1 hour had elapsed since the end of the reaction, Analysis of the exit gas by gas chromatography revealed that the conversion was 100 mol%, and the selectivity of each component was as follows: 1,1,1,4,4,4-hexafluoro-2-butyne (CF3C≡CCF3) was 99.8 mol%, 1,2,3,3,4,4-hexafluoro-1-cyclobutene (c-C4F6) was below the detection limit (ND), 1,1,2,3,3,4,4,4-octafluoro-1-butene (CF2=CFCF2CF3) was 0.0257 mol% (total amount of E-isomer and Z-isomer), 1,1,1,2,4,4,4-heptafluoro-2-butene (CF3CF=CHCF3) was 0.0511 mol% (total amount of E-isomer and Z-isomer), and other by-products were 0.0832 mol% in total.

[0194] Example 1-12: Chromia catalyst; W / F=14.0 g·sec. / cc; 20°C; 11.7 seconds The reaction was carried out using chromia as a catalyst, with a W / F of 14.0 g·sec. / cc and a heating temperature of 20°C. The reaction was carried out in the same manner as in Example 1, except that the reaction time was 11.7 seconds. One hour after the end of the reaction, the gas discharged from the reaction tube was analyzed by gas chromatography, and the conversion rate was 100 molar equivalents. The selectivity of each component was 99.8 mol% for 1,1,1,4,4,4-hexafluoro-2-butyne (CF3C≡CCF3), below the detection limit (ND) for 1,2,3,3,4,4-hexafluoro-1-cyclobutene (c-C4F6), and 0.0187 mol% for 1,1,2,3,3,4,4,4-octafluoro-1-butene (CF2=CFCF2CF3) (E-isomer and The total amount of 1,1,1,2,4,4,4-heptafluoro-2-butene (CF3CF=CHCF3) was 0.0544 mo. % (total amount of E isomer and Z isomer), and the total amount of other by-products was 0.0969 mol %.

[0195] Example 1-13: Chromia catalyst; W / F = 30.0 g·sec. / cc; 50°C; 25.1 seconds The reaction was carried out in the same manner as in Example 1-1, except that a chromia catalyst was used as the catalyst, the heating temperature was set to 50° C., and the reaction was carried out for 25.1 seconds. After 1 hour had elapsed since the end of the reaction, Analysis of the exit gas by gas chromatography revealed that the conversion was 100 mol%, and the selectivity of each component was as follows: 1,1,1,4,4,4-hexafluoro-2-butyne (CF3C≡CCF3) was 99.9 mol%, 1,2,3,3,4,4-hexafluoro-1-cyclobutene (c-C4F6) was below the detection limit (ND), 1,1,2,3,3,4,4,4-octafluoro-1-butene (CF2=CFCF2CF3) was 0.0201 mol% (total amount of E-isomer and Z-isomer), 1,1,1,2,4,4,4-heptafluoro-2-butene (CF3CF=CHCF3) was 0.0387 mol% (total amount of E-isomer and Z-isomer), and other by-products were 0.0012 mol% in total.

[0196] Example 1-14: Chromia catalyst; W / F = 6.0 g·sec. / cc; 150°C; 5.0 seconds The reaction was carried out using chromia as a catalyst, with a W / F of 6.0 g·sec. / cc and a heating temperature of 150°C. The reaction was carried out in the same manner as in Example 1-1, except that the reaction was carried out for 5.0 seconds. One hour after the end of the reaction, the outflow gas from the reaction tube was analyzed by gas chromatography. The conversion was 100 mol %, and the selectivity of each component was 1,1,1,4,4,4-hexafluoro-2-butyne (CF3C≡CCF3 ) is 99.8 mol%, 1,2,3,3,4,4-hexafluoro-1-cyclobutene (c-C4F6) is 0.00311 mol%, 1,1,2,3,3,4,4,4-octafluoro-1-butene (CF2=CFCF2CF3) is 0.0274 mol% (total amount of E-isomer and Z-isomer), and 1,1,1,2,4,4,4-heptafluoro-2-butene (CF3CF=CHCF3) is 0.0477 mol% (total amount of E isomer and Z isomer), and the total amount of other by-products was 0.0818 mol %.

[0197] Example 1-15: Chromia catalyst; W / F = 30.0 g·sec. / cc; 150°C; 25.1 seconds The reaction was carried out for 25.1 seconds using chromia as a catalyst at a heating temperature of 150°C. The reaction was carried out in the same manner as in Example 1-1 except for the above. After 1 hour had elapsed since the end of the reaction, Analysis of the effluent gas by gas chromatography revealed that the conversion was 100 mol% and the selectivity of each component was 99.8 mol% for 1,1,1,4,4,4-hexafluoro-2-butyne (CF3C≡CCF3), 0.00154 mol% for 1,2,3,3,4,4-hexafluoro-1-cyclobutene (c-C4F6), and 0.18 mol% for 1,1,2,3,3,4,4,4-hexafluoro-2-butyne (CF3C≡CCF3). Octafluoro-1-butene (CF2=CFCF2CF3) was 0.0272 mol% (total amount of E- and Z-isomers), and 1,1,1,2,4,4,4-heptafluoro-2-butene (CF3CF=CHCF3) was 0.0364 mol% (total amount of E- and Z-isomers). The total amount of other by-products was 0.125 mol %.

[0198] Example 1-16: Chromia catalyst; W / F = 8.0 g·sec. / cc; 200°C; 6.7 seconds The reaction was carried out for 6.7 seconds using chromia as the catalyst and with a W / F of 8.0 g·sec. / cc. The reaction was carried out in the same manner as in Example 1-1, except that the above-mentioned steps were repeated. After 1 hour had elapsed since the end of the reaction, The effluent gas was analyzed by gas chromatography, and the conversion rate was found to be 99.9 mol %. The selectivity of each component was 99.6 mol% for 1,1,1,4,4,4-hexafluoro-2-butyne (CF3C≡CCF3), 0.00311 mol% for 1,2,3,3,4,4-hexafluoro-1-cyclobutene (c-C4F6), below the detection limit (ND; total amount of E- and Z-isomers) for 1,1,2,3,3,4,4,4-octafluoro-1-butene (CF2=CFCF2CF3), 0.00111 mol% for 1,1,1,2,4,4,4-heptafluoro-2-butene (CF3CF=CHCF3) (total amount of E- and Z-isomers), and 0.416 mol% for other by-products in total.

[0199] Example 1-17: Chromia catalyst; W / F = 16.0 g·sec. / cc; 200°C; 13.3 seconds Chromia catalyst was used as the catalyst, and the reaction was carried out for 13.3 seconds at a W / F of 16.0 g·sec. / cc. The reaction was carried out in the same manner as in Example 1-1, except that the above-mentioned reaction was carried out in the same manner as in Example 1-1. After 1 hour had elapsed since the end of the reaction, Analysis of the effluent gas from these reaction systems by gas chromatography revealed that the conversion was 100 mol%, and the selectivity of each component was as follows: 1,1,1,4,4,4-hexafluoro-2-butyne (CF3C≡CCF3) was 99.9 mol%, 1,2,3,3,4,4-hexafluoro-1-cyclobutene (c-C4F6) was 0.00311 mol%, 1,1,2,3,3,4,4,4-octafluoro-1-butene (CF2=CFCF2CF3) was below the detection limit (ND; total amount of E- and Z-isomers), 1,1,1,2,4,4,4-heptafluoro-2-butene (CF3CF=CHCF3) was 0.00101 mol% (total amount of E- and Z-isomers), and other by-products were 0.0959 mol% in total.

[0200] Example 1-18: Titania catalyst; W / F = 10.0 g·sec. / cc; 200°C; 11.1 seconds Titania catalyst was used as the catalyst, and the reaction was carried out for 11.1 seconds at a W / F of 10.0 g·sec. / cc. The reaction was carried out in the same manner as in Example 1-1, except that the above-mentioned reaction was carried out in the same manner as in Example 1-1. After 1 hour had elapsed since the end of the reaction, The effluent gas from the reactor was analyzed by gas chromatography, and the conversion rate was found to be 99.0 mol%. The selectivity of each component was 99.4 mol% for 1,1,1,4,4,4-hexafluoro-2-butyne (CF3C≡CCF3), 0.254 mol% for 1,2,3,3,4,4-hexafluoro-1-cyclobutene (c-C4F6), 0.059 mol% for 1,1,2,3,3,4,4,4-octafluoro-1-butene (CF2=CFCF2CF3) (ND; total amount of E- and Z-isomers), and 0.0341 mol% for 1,1,1,2,4,4,4-heptafluoro-2-butene (CF3CF=CHCF3) (total amount of E- and Z-isomers). The total amount of other by-products was 0.213 mol %.

[0201] Example 1-19: Titania catalyst; W / F = 14.0 g·sec. / cc; 200°C; 15.5 seconds Titania catalyst was used as the catalyst, and the reaction was carried out for 15.5 seconds at a W / F of 14.0 g·sec. / cc. The reaction was carried out in the same manner as in Example 1-1, except that the above-mentioned reaction was carried out in the same manner as in Example 1-1. After 1 hour had elapsed since the end of the reaction, The effluent gas from the reactor was analyzed by gas chromatography, and the conversion rate was found to be 99.0 mol%. The selectivity of each component was 99.3 mol% for 1,1,1,4,4,4-hexafluoro-2-butyne (CF3C≡CCF3), 0.362 mol% for 1,2,3,3,4,4-hexafluoro-1-cyclobutene (c-C4F6), and 0.0587 mol% for 1,1,2,3,3,4,4,4-octafluoro-1-butene (CF2=CFCF2CF3) (ND; the total amount of E and Z isomers). ), 1,1,1,2,4,4,4-heptafluoro-2-butene (CF3CF=CHCF3) was 0.0321 mol% (E and Z forms) The total amount of by-products was 0.247 mol %.

[0202] Example 1-20: Silica-alumina catalyst; W / F = 7.5 g·sec. / cc; 20°C; 14.9 seconds The reaction was carried out in the same manner as in Example 1-1, except that a silica-alumina catalyst was used as the catalyst, the W / F was 7.5 g·sec. / cc, the heating temperature was 20°C, and the reaction was carried out for 14.9 seconds. After the time had elapsed, the outflow gas from the reaction tube was analyzed by gas chromatography. The conversion rate was 100 mol % and the selectivity of each component was 1,1,1,4,4,4-hexafluoro-2-butyne (CF ≡CCF3) was 99.4 mol%, 1,2,3,3,4,4-hexafluoro-1-cyclobutene (c-C4F6) was below detection limit (ND), and 1,1,2,3,3,4,4,4-octafluoro-1-butene (CF2=CFCF2CF3) was at detection limit. The content of 1,1,1,2,4,4,4-heptafluoro-2-butene (CF3CF=CHCF3) was 0.0909 mol % (total amount of E- and Z-isomers), and the total amount of other by-products was 0.504 mol %. .

[0203] Example 1-21: Silica-alumina catalyst; W / F = 15.0 g·sec. / cc; 20°C; 29.9 seconds A silica-alumina catalyst was used as the catalyst, and the W / F was set to 15.0 g·sec. / cc and the heating temperature was set to 20°C. The reaction was carried out in the same manner as in Example 1-1, except that the reaction was carried out for 29.9 seconds at 100° C. for 29.9 seconds. One hour after the end of the reaction, the gas discharged from the reaction tube was analyzed by gas chromatography. The conversion rate was 100 mol%, and the selectivity of each component was 99.9 mol% for 1,1,1,4,4,4-hexafluoro-2-butyne (CF3C≡CCF3), and 1,2,3,3,4,4-hexafluoro-1-cyclobutene (c-C4F6) was detected. Below the limit (ND), 1,1,2,3,3,4,4,4-octafluoro-1-butene (CF2 = CFCF2CF3) was 0.00688 mol% (total amount of E and Z isomers), 1,1,1,2,4,4,4-heptafluoro-2-butene (CF3CF = CHCF3 ) was 0.0555 mol % (total amount of E isomer and Z isomer), and the total amount of other by-products was 0.0374 mol %.

[0204] Example 1-22: Silica-alumina catalyst; W / F = 30.0 g·sec. / cc; 20°C; 59.8 seconds The reaction was carried out in the same manner as in Example 1-1, except that a silica alumina catalyst was used as the catalyst, the heating temperature was set to 20° C., and the reaction was carried out for 59.8 seconds. After 1 hour had elapsed since the end of the reaction, Analysis of the effluent gas from these reaction systems by gas chromatography revealed that the conversion was 100 mol%, and the selectivity of each component was as follows: 1,1,1,4,4,4-hexafluoro-2-butyne (CF3C≡CCF3) was 99.8 mol%, 1,2,3,3,4,4-hexafluoro-1-cyclobutene (c-C4F6) was below the detection limit (ND), 1,1,2,3,3,4,4,4-octafluoro-1-butene (CF2=CFCF2CF3) was below the detection limit (ND; total amount of E- and Z-isomers), 1,1,1,2,4,4,4-heptafluoro-2-butene (CF3CF=CHCF3) was 0.0804 mol% (total amount of E- and Z-isomers), and other by-products were 0.161 mol% in total.

[0205] Example 1-23: Silica-alumina catalyst; W / F = 4.0 g sec. / cc; 100°C; 8.0 seconds A silica-alumina catalyst was used as the catalyst, and the W / F was set to 4.0 g·sec. / cc and the heating temperature was set to 100°C. The reaction was carried out in the same manner as in Example 1, except that the reaction was carried out for 8.0 seconds. After the reaction, the outflow gas from the reaction tube was analyzed by gas chromatography. The conversion was 100 mol%, and the selectivity of each component was 99.4 mol% for 1,1,1,4,4,4-hexafluoro-2-butyne (CF3C≡CCF3), 0.00121 mol% for 1,2,3,3,4,4-hexafluoro-1-cyclobutene (c-C4F6), and 1,1,2,3,3,4,4,4-octafluoro-1-butene (CF2=CFCF2CF3) was below the detection limit (ND; E The content of 1,1,1,2,4,4,4-heptafluoro-2-butene (CF3CF=CHCF3) was 0.0909 mol % (total amount of E isomer and Z isomer), and the total amount of other by-products was 0.503 mol %.

[0206] Example 1-24: Silica-alumina catalyst; W / F = 4.0 g·sec. / cc; 200°C; 8.0 seconds The reaction was carried out for 8.0 seconds using a silica-alumina catalyst with a W / F of 4.0 g·sec. / cc. The reaction was carried out in the same manner as in Example 1-1, except that the reaction was carried out in the same manner as in Example 1-1. Analysis of the gas effluent from the tube by gas chromatography revealed that the conversion was 100 mol % and the selectivity of each component was 99.5 mol % for 1,1,1,4,4,4-hexafluoro-2-butyne (CF3C≡CCF3). %, 1,2,3,3,4,4-hexafluoro-1-cyclobutene (c-C4F6) was 0.0670 mol%, 1,1,2,3,3,4,4,4-octafluoro-1-butene (CF2=CFCF2CF3) was below the detection limit (ND; total amount of E and Z isomers), and 1,1,1,2,4,4,4-heptafluoro-2-butene (CF3CF=CHCF3) was 0.0101 mol% (E and Z isomers). The total amount of the Z isomer was 0.467 mol %.

[0207] Example 1-25: Silica-alumina catalyst; W / F = 8.0 g·sec. / cc; 200°C; 16.0 seconds The reaction was carried out in the same manner as in Example 1-1, except that a silica-alumina catalyst was used as the catalyst, the W / F was set to 8.0 g·sec. / cc, and the reaction was carried out for 16.0 seconds. One hour after the end of the reaction, Analysis of the gas effluent from the reaction tube by gas chromatography revealed that the conversion was 100 mol%, and the selectivity of each component was 99.5 mol% for 1,1,1,4,4,4-hexafluoro-2-butyne (CF3C≡CCF3), 0.0611 mol% for 1,2,3,3,4,4-hexafluoro-1-cyclobutene (c-C4F6), and below the detection limit for 1,1,2,3,3,4,4,4-octafluoro-1-butene (CF2=CFCF2CF3) (ND; E and Z isomers were not detected). The content of 1,1,1,2,4,4,4-heptafluoro-2-butene (CF3CF=CHCF3) was 0.00921 mol % (total amount of E isomer and Z isomer), and the total amount of other by-products was 0.480 mol %.

[0208] The results of Examples 1-1 and 1-10 to 1-17 are shown in Table 2, and the results of Examples 1-18 to 1-25 are shown in Table 3.

[0209] [Table 2]

[0210] [Table 3]

[0211] [Example 2: Requirements (C) to (F)] In the following Example 2, the following catalyst was used: Fluorinated chromia catalyst (1): Chromia fluorinated with hydrogen fluoride; pore volume 0.10 mL / g; Chromia (Cr2O3; pore volume 0.15 mL / g) was fluorinated by passing hydrogen fluoride through it at atmospheric pressure at 100 to 400°C for 6 hours. Fluorinated chromia catalyst (2): Chromia fluorinated with chlorodifluoromethane (R22) Chromia (Cr2O3; pore volume 0.15mL / g) was fluorinated by passing chlorodifluoromethane (R22) through it at atmospheric pressure at 100 to 500°C for 6 hours. Fluorinated silica-alumina catalyst (1): Silica-alumina fluorinated with hydrogen fluoride; pore volume 0.55 mL / g; For silica-alumina (pore volume 0.70 mL / g), 6 The mixture was fluorinated by passing hydrogen fluoride through it for 2 hours. Fluorinated silica-alumina catalyst (2): Silica fluorinated with chlorodifluoromethane (R22) Fluorination was carried out by passing chlorodifluoromethane (R22) through silica alumina (pore volume 0.70 mL / g) at atmospheric pressure at 100 to 500°C for 6 hours.

[0212] In addition, the fluorinated alumina catalyst was fluorinated by passing hydrogen fluoride through the specified alumina at atmospheric pressure at 100 to 400°C for 6 hours. The details of the catalyst are shown in Table 4.

[0213] [Table 4]

[0214] Example 2-1: R22 fluorinated chromia catalyst; pore volume 0.13 mL / g As a catalyst, fluorinated chromia catalyst (2) (fluorine in chlorodifluoromethane (R22) A metal tubular reactor was filled with hexafluorobutadiene (CF2CF=CFCF2) and the reaction proceeded in a continuous gas phase flow system by heating the reaction tube to 200°C and supplying hexafluorobutadiene (CF2CF=CFCF2) to the reaction tube so that the W / F was 8 g·sec. / cc. After a certain period of time had elapsed, the gas discharged from the reaction tube was analyzed by gas chromatography. As a result, the catalyst deterioration rate was found to be -0.12% / hour. The catalyst deterioration rate is the slope of a plot with reaction time on the horizontal axis and conversion rate on the vertical axis. The results are shown in Table 5.

[0215] [Table 5]

[0216] Example 2-2: R22 fluorinated silica alumina catalyst; pore volume 0.69 mL / g The only difference is that the catalyst used is a fluorinated silica alumina catalyst (2) (silica alumina fluorinated with chlorodifluoromethane (R22)) instead of a fluorinated chromia catalyst (2). The reaction was carried out in the same manner as in Example 2-1. After a predetermined time had elapsed, the gas discharged from the reaction tube was analyzed by gas chromatography. As a result, the catalyst deterioration rate was -0.0014% / hour. The catalyst deterioration rate is calculated by plotting the reaction time on the horizontal axis and the conversion rate on the vertical axis. The results are shown in Table 6.

[0217] [Table 6]

[0218] Example 2-3: Fluorinated alumina catalyst; pore volume 1.33 mL / g The reaction was carried out in the same manner as in Example 2-1, except that the fluorinated alumina catalyst (1) was used as the catalyst instead of the fluorinated chromia catalyst (2). After a predetermined time had elapsed, the gas discharged from the reaction tube was analyzed by gas chromatography. As a result, the catalyst deterioration rate was -0.025% / hour. The catalyst deterioration rate means the slope when the reaction time is plotted on the horizontal axis and the conversion rate is plotted on the vertical axis. The results are shown in Table 7.

[0219] [Table 7]

[0220] Example 2-4: Fluorinated alumina catalyst; pore volume 0.43 mL / g The reaction was carried out in the same manner as in Example 2-1, except that the fluorinated alumina catalyst (2) was used as the catalyst instead of the fluorinated chromia catalyst (2). After a predetermined time had elapsed, the gas discharged from the reaction tube was analyzed by gas chromatography. As a result, the catalyst deterioration rate was -0.026% / hour. The catalyst deterioration rate means the slope when the reaction time is plotted on the horizontal axis and the conversion rate is plotted on the vertical axis. The results are shown in Table 8.

[0221] [Table 8]

[0222] Comparative Example 2-1: Fluorinated alumina catalyst; pore volume 0.22 mL / g The reaction was carried out in the same manner as in Example 2-1, except that the fluorinated alumina catalyst (3) was used as the catalyst instead of the fluorinated chromia catalyst (2). After a predetermined time had elapsed, the gas discharged from the reaction tube was analyzed by gas chromatography. As a result, the catalyst deterioration rate was -0.65% / The catalyst deterioration rate is the slope of a plot with reaction time on the horizontal axis and conversion rate on the vertical axis. The results are shown in Table 9.

[0223] [Table 9]

[0224] Example 2-5: Fluorinated alumina catalyst; pore volume 0.39 mL / g The reaction was carried out in the same manner as in Example 2-1, except that the fluorinated alumina catalyst (4) was used as the catalyst instead of the fluorinated chromia catalyst (2). After a predetermined time had elapsed, The outflow gas was analyzed by gas chromatography. The catalyst deterioration rate was -0.29% / The catalyst deterioration rate is the slope of a plot with reaction time on the horizontal axis and conversion rate on the vertical axis. The results are shown in Table 10.

[0225] [Table 10]

[0226] Comparative Example 2-2: Fluorinated alumina catalyst; pore volume 0.23 mL / g The reaction was carried out in the same manner as in Example 2-1, except that the fluorinated alumina catalyst (5) was used as the catalyst instead of the fluorinated chromia catalyst (2). After a predetermined time had elapsed, the gas discharged from the reaction tube was analyzed by gas chromatography. As a result, the catalyst deterioration rate was -0.67% / hour. The catalyst deterioration rate is the slope of a plot with reaction time on the horizontal axis and conversion rate on the vertical axis. The results are shown in Table 11.

[0227] [Table 11]

[0228] Of the results in Tables 7 to 11 above, the relationship between the elapsed time (contact time) and the conversion rate is shown in FIG. 1, the relationship between the pore volume before fluorination and the deterioration rate is shown in FIG. 2, and the relationship between the pore volume after fluorination and the deterioration rate is shown in FIG. 3.

[0229] [Example 3: Requirement (G)] In the following Example 3, a chromia catalyst (Cr2O3) or an alumina catalyst (Al2O3) was used as the catalyst.

[0230] The water content of the hexafluorobutadiene was adjusted to a predetermined water content by adding water or by dehydrating with a molecular sieve, and the water content was measured by the Karl Fischer method.

[0231] Example 3-1: Chromia catalyst; water content 20 ppm Nitrogen gas was filled into a metal tubular reactor to create a nitrogen gas atmosphere, and then chromia catalyst was added as a catalyst. The reactor tube was heated to 200°C and heated with a heater so that the W / F was 8g·sec. / cc. By supplying fluorobutadiene (CF2CF=CFCF2) to the reaction tube, the reaction is carried out in a gas phase continuous flow system. The water content of the hexafluorobutadiene at the start of the reaction was 20 ppm by mass. The water content in the reaction system was adjusted to 20 ppm from the start of the reaction to the end of the reaction. After filtering, the gas discharged from the reaction tube was analyzed by gas chromatography. The result was that the catalyst deterioration rate was -0.12% / hour. The catalyst deterioration rate is shown on the horizontal axis as reaction time and on the vertical axis as reaction time. The results are shown in Table 12.

[0232] [Table 12]

[0233] Example 3-2: Chromia catalyst; water content 2 ppm The water content of hexafluorobutadiene at the start of the reaction is 20 ppm by mass. The water content of hexafluorobutadiene at the start of the reaction is 2 mass % instead of orobutadiene. The reaction system from the start to the end of the reaction using hexafluorobutadiene with a concentration of ppm The reaction was carried out in the same manner as in Example 3-1, except that the water content in the reaction tube was adjusted to 2 ppm. After a predetermined time had elapsed, the gas discharged from the reaction tube was analyzed by gas chromatography. The catalyst deterioration rate was -0.12% / hour. The catalyst deterioration rate is shown on the horizontal axis as reaction time and on the vertical axis as The results are shown in Table 13.

[0234] [Table 13]

[0235] Example 3-3: Alumina catalyst; water content 20 ppm The reaction was carried out in the same manner as in Example 3-1, except that an alumina catalyst was used instead of a chromia catalyst. After a predetermined time had elapsed, the gas discharged from the reaction tube was analyzed by gas chromatography. As a result, the catalyst deterioration rate was -0.0302% / hour. The axis indicates the reaction time and the vertical axis indicates the conversion rate. The results are shown in Table 14.

[0236] [Table 14]

[0237] Example 3-4: Alumina catalyst; water content 2 ppm An alumina catalyst is used instead of a chromia catalyst, and the water content of hexafluorobutadiene at the start of the reaction is 20 ppm by mass instead of hexafluorobutadiene at the start of the reaction. The reaction was carried out in the same manner as in Example 3-1, except that the amount of water in the reaction system was adjusted to 2 ppm from the start of the reaction to the end of the reaction by using hexafluorobutadiene having a water content of 2 ppm by mass. After a predetermined time had elapsed, the gas discharged from the reaction tube was analyzed by gas chromatography. As a result, the deterioration rate of the catalyst was -0.08% / hour. The catalyst deterioration rate is the slope of a plot of reaction time on the horizontal axis and conversion rate on the vertical axis. The results are shown in Table 15.

[0238] [Table 15]

Claims

1. A method for producing a perfluoroalkyne compound, comprising the steps of: A step of reacting a perfluoroalkadiene compound in the presence of a catalyst to obtain a perfluoroalkyne compound. Equipped with the following (A) to (G): (A) the catalyst contains at least one catalyst selected from the group consisting of a catalyst containing a transition metal element and a catalyst containing at least two elements belonging to Groups 3 to 14 of the periodic table; (B) The catalyst contains at least one element belonging to Groups 3 to 14 of the Periodic Table. death, the contact time between the catalyst and the perfluoroalkadiene compound represented by the general formula (2) is 30 seconds or less; (C) The catalyst is a fluorinated chromium oxide having a pore volume of 0.08 mL / g or more, a fluorinated alumina having a pore volume of 0.35 mL / g or more, and a fluorinated silica having a pore volume of 0.50 mL / g or more. At least one catalyst selected from the group consisting of silica and alumina, (D) the catalyst contains a fluorinated metal oxide having a pore volume of 0.35 mL / g or more; (E) The catalyst is a hydrofluorocarbon, a hydrochlorofluorocarbon, or a chlorofluorocarbon. At least one compound selected from the group consisting of fluorocarbons and a metal oxide. containing a metal oxide fluorinated by reacting (F) The catalyst comprises a chromium oxide having a pore volume of 0.10 mL / g or more, an alumina having a pore volume of 0.45 mL / g or more, A catalyst containing at least one metal oxide fluorinated catalyst selected from the group consisting of lumina and silica alumina having a pore volume of 0.50 mL / g or more. (G) Perfluoroalkadiene at least partially from the start of the reaction to the end of the reaction The mass of the compound is taken as the standard (100 mass%), and the water content in the reaction system is 30 mass ppm or less. reacting the perfluoroalkadiene compound; A manufacturing method that satisfies any one of the above.

2. The perfluoroalkyne compound is represented by the general formula (1): CR 1 2 R 2 -C≡C-CR 3 R 4 2 (1) [In the formula, R 1 ~R 4 and each of the formula (I) is the same or different and represents a fluorine atom or a perfluoroalkyl group.

3. The perfluoroalkadiene compound is General formula (2): CR 1 2 =CR 2 -CR 3 =CR 4 2 (2) [In the formula, R 1 ~R 4 and each of the formula (I) is the same or different and represents a fluorine atom or a perfluoroalkyl group.

4. The catalyst satisfies the above (A) or (B) and contains at least one transition metal element belonging to Groups 4 to 6 of the periodic table, and the catalyst also contains at least one transition metal element belonging to Groups 4 to 6 and Groups 13 to 14 of the periodic table. The method according to any one of claims 1 to 3, wherein the catalyst is at least one selected from the group consisting of catalysts containing at least two of the elements listed above.

5. The production method according to any one of claims 1 to 4, which satisfies either (A) or (B) and is at least one catalyst selected from the group consisting of an optionally fluorinated chromium oxide catalyst, an optionally fluorinated titanium oxide catalyst, an optionally fluorinated zirconia catalyst, and an optionally fluorinated silica-alumina catalyst.

6. The method according to any one of claims 1 to 3, which satisfies the condition (D) and in which the metal constituting the fluorinated metal oxide includes at least one element belonging to Groups 3 to 14 of the periodic table. Manufacturing method.

7. The (E) is satisfied, and the pore volume of the metal oxide before being fluorinated is 0.45 mL / g or more. The method according to any one of claims 1 to 3, wherein

8. The condition (E) is satisfied, and the metal constituting the metal oxide before fluorination is a periodic The method according to claim 1, 2, 3 or 7, wherein the composition contains at least one element belonging to groups 3 to 14 of the table.

9. 4. The method according to claim 1, wherein the condition (G) is satisfied and the catalyst contains at least one element belonging to Groups 3 to 14 of the periodic table.

10. The process according to any one of claims 1 to 9, wherein the reaction of the perfluoroalkadiene compound is carried out in a gas phase.

11. 11. The reaction of the perfluoroalkadiene compound is carried out at 170° C. or higher. The method for producing a semiconductor device according to any one of claims 1 to 5,

12. The method according to any one of claims 1 to 11, wherein a perfluorocycloalkene compound is also produced in addition to the perfluoroalkyne compound by the reaction of the perfluoroalkadiene compound.

13. The perfluorocycloalkene compound is Formula (3): 【Chemistry 1】 [In the formula, R 1 ~R 4 is the same as above.] The method according to claim 12, wherein the perfluorocycloalkene compound is represented by the formula:

14. A method for producing a perfluoroalkyne compound, comprising the steps of: A production method comprising a step of obtaining the perfluoroalkadiene compound by using a perfluorocycloalkene compound produced as a by-product by the production method according to claim 12 or 13 as a substrate.

15. The perfluoroalkyne compound is represented by the general formula (1): CR 1 2 R 2 -C≡C-CR 3 R 4 2 (1) [In the formula, R 1 ~R 4 and each of the formula (I) is the same or different and represents a fluorine atom or a perfluoroalkyl group.

16. General formula (1): CR 1 2 R 2 -C≡C-CR 3 R 4 2 (1) [In the formula, R 1 ~R 4 and each may be the same or different and represent a fluorine atom or a perfluoroalkyl group. General formula (3): 【Chemistry 2】 [In the formula, R 1 ~R 4 is the same as above.] A composition containing a perfluorocycloalkene compound represented by the formula: The total amount of the composition is taken as 100 mol %, and the perfluoroalkyne compound represented by the general formula (1) is The composition, wherein the content is 40 to 99.999 mol %.

17. 17. The composition of claim 16 for use as an etching gas or a building block for organic synthesis.

18. A catalyst used to obtain a perfluoroalkyne compound by reacting a perfluoroalkadiene compound, comprising the following (C) to (D): (C) Fluorinated chromium oxide having a pore volume of 0.08 mL / g or more, and a pore volume of 0.35 mL / g or more Contains at least one selected from the group consisting of fluorinated alumina and fluorinated silica alumina having a pore volume of 0.50 mL / g or more; (D) containing a fluorinated metal oxide having a pore volume of 0.35 mL / g or more; A catalyst that satisfies any of the following criteria:

19. 19. The catalyst according to claim 18, which satisfies the condition (D) and wherein the metal constituting the fluorinated metal oxide includes at least one element belonging to Groups 3 to 14 of the periodic table.

20. A method for producing a catalyst used to obtain a perfluoroalkyne compound by reacting a perfluoroalkadiene compound, comprising the steps of: (E) Hydrofluorocarbons, hydrochlorofluorocarbons and chlorofluorocarbons At least one compound selected from the group consisting of carbon and a metal oxide is reacted with the compound. fluorinating the metal oxide by (F) Chromium oxide having a pore volume of 0.10 mL / g or more, alumina having a pore volume of 0.45 mL / g or more, and At least one metal selected from the group consisting of silica alumina having a pore volume of 0.50 mL / g or more Fluorinating the oxide A manufacturing method comprising any one of the steps.

21. The (E) is satisfied, and the pore volume of the metal oxide before being fluorinated is 0.45 mL / g or more. The method of claim 20, wherein

22. The condition (E) is satisfied, and the metal constituting the metal oxide before fluorination is a periodic The method according to claim 20 or 21, comprising at least one element belonging to groups 3 to 14 of the table.

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