Method for producing perfluoroalkyne compound

Abstract

FIELD: method for producing a perfluoroalkyne compound.SUBSTANCE: introducing a perfluoroalkadiene compound into a reaction in the presence of a catalyst in order to obtain a perfluoroalkyne compound and satisfying the following condition (G): (G) at least a part of the reaction of the perfluoroalkadiene compound from the beginning to the end of the reaction is carried out under conditions in which the water content in the reaction system is 30 ppm by weight or less based on the weight of the perfluoroalkadiene compound, taken as 100% by weight. Moreover, the catalyst contains at least one element that belongs to groups 4-6 and groups 13-14 of the periodic table. The invention also relates to a method for producing a perfluoroalkyne compound, which includes obtaining a perfluoroalkadiene compound using a perfluorocycloalkene compound obtained as a by-product in the method as a substrate.EFFECT: use of the proposed invention makes it possible to obtain the target compound with high selectivity.9 cl, 3 dwg, 15 tbl, 3 ex

Description

[0001] This invention relates to a method for producing a perfluoroalkyne compound.Background of the invention

[0002] Perfluoroalkyne compounds are compounds expected to be useful as dry etching gases for semiconductors, as well as in various applications such as cooling agents, foaming agents, and heat transfer fluids. Perfluoroalkyne compounds are compounds that contain a carbon-carbon triple bond.

[0003] As a method for producing such a perfluoroalkyne compound, an isomerization reaction of hexafluorobutadiene is known. For example, Patent Document (PD) 1 discloses the isomerization of hexafluorobutadiene to produce hexafluorobutyne using halogenated alumina. Patent Document (PD) 2 discloses the use of sodium fluoride or a mixture containing sodium fluoride as a catalyst for the isomerization reaction to produce hexafluorobutyne from hexafluorocyclobutene. Citation ListPatent Documents

[0004] PD 1: JP 2012-001448 APD 2: JP 2014-058488 A. The essence of the invention Technical problem

[0005] The objective of the present invention is to develop a method that can produce a perfluoroalkyne compound with high selectivity at a high reaction conversion rate and which is less likely to produce a fluoroalkene compound as a by-product. Another objective of the present invention is to develop a method for producing a perfluoroalkyne compound, wherein the method is capable of reducing the degradation (i.e., deterioration of properties) of the catalyst. Solution to the problem

[0006] The present invention includes the following objects.

[0007] Item 1. A method for producing a perfluoroalkyne compound, which comprises reacting a perfluoroalkadiene compound in the presence of a catalyst to obtain the perfluoroalkyne compound and satisfying one of the following conditions (A) to (G): (A) the catalyst comprises at least one catalyst selected from the group consisting of catalysts containing a transition metal element and catalysts containing at least two elements that belong to groups 3 to 14 of the periodic table of the elements; (B) the catalyst comprises a catalyst containing at least one element that belongs 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;(C) the catalyst comprises at least one catalyst selected from the group consisting of a fluorinated chromium oxide having a porosity of 0.08 ml / g or greater, a fluorinated aluminum oxide having a porosity of 0.35 ml / g or greater, and a fluorinated aluminosilicate having a porosity of 0.50 ml / g or greater;(D) the catalyst comprises a fluorinated metal oxide having a porosity of 0.35 ml / g or greater;(E) the catalyst comprises a metal oxide fluorinated by reacting the metal oxide with at least one compound selected from the group consisting of a hydrofluorocarbon, a hydrochlorofluorocarbon, and a chlorofluorocarbon;(F) the catalyst comprises one or more catalysts obtained by fluorinating at least one metal oxide selected from the group consisting of a chromium oxide having a porosity of 0.10 ml / g or greater, an aluminum oxide having a porosity 0.45 ml / g or more, and an aluminosilicate having a porosity of 0.50 ml / g or more;and(G) at least a part of the reaction of the perfluoroalkadiene compound from the beginning to the end of the reaction is carried out under conditions in which the water content in the reaction system is 30 ppm by weight or less based on the weight of the perfluoroalkadiene compound (taken as 100% by weight);

[0008] Item 2. The production method according to item 1, wherein the perfluoroalkyne compound is represented by formula (1): (where the substituents R 1 -R 4 are the same or different and represent a fluorine atom or a perfluoroalkyl group).

[0009] Item 3. The production method according to item 1 or 2, wherein the perfluoroalkadiene compound is represented by formula (2): (where the substituents R 1 -R 4 are the same or different and represent a fluorine atom or a perfluoroalkyl group).

[0010] Item 4. The production method according to any one of items 1 to 3, wherein the method satisfies the condition (A) or (B) and the catalyst is at least one catalyst selected from the group consisting of: a catalyst containing at least one transition metal element that belongs to groups 4 to 6 of the periodic table; and a catalyst containing at least two elements that belong to groups 4 to 6 and groups 13 and 14 of the periodic table.

[0011] Item 5. The production method according to any one of items 1 to 4, wherein the method satisfies the condition (A) or (B), and the catalyst is at least one catalyst selected from the group consisting of optionally fluorinated chromium oxide catalysts, optionally fluorinated titanium oxide catalysts, optionally fluorinated zirconium oxide catalysts, and optionally fluorinated aluminosilicate catalysts.

[0012] Item 6. The production method according to any one of items 1 to 3, wherein the method satisfies the condition (D), and the metal of the fluorinated metal oxide includes at least one element that belongs to groups 3 to 14 of the periodic table.

[0013] Item 7. The production method according to any one of items 1 to 3, wherein the method satisfies the condition (E), and the metal oxide before fluorination has a porosity of 0.45 ml / g or more.

[0014] Item 8. The production method according to item 1, 2, 3 or 7, wherein the method satisfies the condition (E), and the metal of the metal oxide before fluorination includes at least one element that belongs 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 method satisfies the condition (G), and the catalyst contains at least one element that belongs to groups 3 to 14 of the Periodic Table.

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

[0017] Item 11. The production method according to any one of items 1 to 10, wherein the reaction of the perfluoroalkadiene compound is carried out at a temperature of 170°C or higher.

[0018] Item 12. The production method according to any one of items 1 to 11, wherein the reaction of the perfluoroalkadiene compound produces a perfluorocycloalkene compound in addition to the perfluoroalkyne compound.

[0019] Item 13. The production method according to item 12, wherein the perfluorocycloalkene compound is represented by formula (3):

[0020]

[0021] (where the substituents R 1 -R 4 have the meanings defined above).

[0022] Item 14. A method for producing a perfluoroalkyne compound, which comprises producing a perfluoroalkadiene compound using as a substrate a perfluorocycloalkene compound obtained as a by-product in the production method of item 12 or 13.

[0023] Item 15. The production method according to item 14, wherein the perfluoroalkyne compound is represented by formula (1): (where the substituents R 1 -R 4 are the same or different and represent a fluorine atom or a perfluoroalkyl group).

[0024] Item 16. A composition containing a perfluoroalkyne compound and a perfluorocycloalkene compound, wherein the perfluoroalkyne compound is represented by formula (1): (where the substituents R 1 -R 4are the same or different and represent a fluorine atom or a perfluoroalkyl group), the perfluorocycloalkene compound is represented by formula (3):

[0025]

[0026] (where the substituents R 1 -R 4 have the meanings defined above), and the composition contains a perfluoroalkyne compound represented by formula (1) in an amount of from 40 to 99.999 mol.% based on the total amount of the composition, taken as 100 mol.%.

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

[0028] Item 18. A catalyst for use in the reaction of a perfluoroalkadiene compound to produce a perfluoroalkyne compound, wherein the catalyst satisfies the following conditions (C) or (D): (C) the catalyst contains at least one component selected from the group consisting of a fluorinated chromium oxide having a porosity of 0.08 ml / g or more, a fluorinated aluminum oxide having a porosity of 0.35 ml / g or more, and a fluorinated aluminosilicate having a porosity of 0.50 ml / g or more; (D) the catalyst contains a fluorinated metal oxide having a porosity of 0.35 ml / g or more.

[0029] Item 19. The catalyst according to item 18, wherein the catalyst satisfies the condition (D), and the metal of the fluorinated metal oxide includes at least one element that belongs to groups 3 to 14 of the periodic table.

[0030] Item 20. A method for producing a catalyst for use in a reaction of a perfluoroalkadiene compound to produce a perfluoroalkyne compound, comprising the following step (E) or (F): (E) reacting a metal oxide with at least one compound selected from the group consisting of a hydrofluorocarbon, a hydrochlorofluorocarbon, and a chlorofluorocarbon to thereby fluorinate the metal oxide; (F) fluorinating at least one metal oxide selected from the group consisting of chromium oxide having a porosity of 0.10 ml / g or more, aluminum oxide having a porosity of 0.45 ml / g or more, and aluminosilicate having a porosity of 0.50 ml / g or more.

[0031] Item 21. The production method according to item 20, wherein the method satisfies the condition (E), and the metal oxide before fluorination has a porosity of 0.45 ml / g or more.

[0032] Item 22. The production method according to item 20 or 21, wherein the method satisfies the condition (E) and the metal of the metal oxide before fluorination includes at least one element that belongs to groups 3 to 14 of the periodic table. Advantageous effects of the invention

[0033] According to the present invention, a production method can be provided that is capable of producing a perfluoroalkyne compound with high selectivity at a high reaction conversion and is less likely to produce a fluoroalkene compound as a by-product. According to the present invention, a method for producing a perfluoroalkyne compound can also be provided, wherein the method is capable of reducing catalyst degradation. Brief Description of the Drawings

[0034] FIG. 1: Relationship between reaction time and conversion rate using a fluorinated alumina catalyst.FIG. 2: Relationship between porosity before fluorination and degradation rate using a fluorinated alumina catalyst.FIG. 3: Relationship between porosity after fluorination and degradation rate using a fluorinated alumina catalyst.Description of Embodiments

[0035] In this specification, the terms "comprises," "is located," and "includes" encompass the concepts of "comprising," "consisting essentially of," and "consisting of." In this specification, a numerical range indicated as "from A to B" means A or greater and B or less.

[0036] 1. Catalyst and method for producing a catalystThe catalyst according to the present invention is a catalyst for use in reacting a perfluoroalkadiene compound to produce a perfluoroalkyne compound, wherein the catalyst satisfies the following conditions (C) or (D): (C) the catalyst contains at least one component selected from the group consisting of a fluorinated chromium oxide having a porosity of 0.08 ml / g or more, a fluorinated aluminum oxide having a porosity of 0.35 ml / g or more, and a fluorinated aluminosilicate having a porosity of 0.50 ml / g or more;

[0037] [1-1] Catalyst and Method for Producing the Catalyst (No. 1) In the present invention, a catalyst 1 for use in reacting (isomerizing) a perfluoroalkadiene compound to produce a perfluoroalkyne compound (which may be referred to as "isomerization reaction catalyst 1" hereinafter) contains at least one component selected from the group consisting of a fluorinated chromium oxide having a porosity of 0.08 ml / g or more, a fluorinated alumina having a porosity of 0.35 ml / g or more, and a fluorinated aluminosilicate having a porosity of 0.50 ml / g or more. This catalyst satisfies the above-described requirement (C). Conventionally used isomerization reaction catalysts are not optimized in porosity. It is unclear what porosity of a catalyst is usually used.In the present invention, fluorinated metal oxides having specific porosity values ​​are used to increase the reaction conversion and reduce catalyst degradation; accordingly, even when the isomerization reaction is carried out for a long period of time, catalyst degradation can be slowed down. Therefore, the use of the catalyst according to the present invention can reduce the frequency of catalyst replacement and is thus economical.

[0038] The chromium oxide catalyst is not particularly limited. When the chromium oxide is expressed as CrO m , the preferred ratio is 1 <m<3, более предпочтительным 1,2<m<2 и даже более предпочтительным 1,3<m<1,8. Когда оксид хрома выражен в виде CrO m ⋅nH2O, chromium oxide can be hydrogenated to achieve an n value of 3 or less and especially in the range of 1 to 1.5.

[0039] Below is an example of the method for synthesizing chromium oxide catalyst.

[0040] First, an aqueous solution of a chromium salt (chromium nitrate, chromium chloride, chromium alum, chromium sulfate, etc.) is mixed with aqueous ammonia to form a precipitate of chromium hydroxide. The precipitation reaction rate at this time controls the physical properties of the chromium hydroxide. A high reaction rate is preferable. The reaction rate depends on the temperature of the reaction solution, the mixing method of the ammonia water (mixing speed), the stirring state, etc.

[0041] This precipitate can be filtered and washed, and then dried. Drying can be carried out, for example, in air at a temperature of from 70 to 200 °C for from 1 to 100 hours. The catalyst at this stage can be called a catalyst in the chromium hydroxide state. Then, the catalyst can be ground. From the viewpoint of granule strength, catalyst activity, etc., the precipitation reaction rate is preferably controlled so that the ground powder (for example, a powder having a particle size of 1000 μm or less, in particular, a particle size of from 4.6 to 1000 μm in the 95% fraction) has a particle density of from 0.6 to 1.1 g / ml, and preferably from 0.6 to 1.0 g / ml. The powder preferably has a specific surface area (specific surface area) determined by the BET method of 100 m 2 / g or more, more preferably 120 m 2 / g or more, for example, at 200°C under degassing conditions for 80 min. The upper limit of the specific surface area is, for example, approximately 220 m 2 / G.

[0042] If necessary, graphite can be mixed into chromium hydroxide powder at a rate of 3% by weight or less and granulated using a tableting machine. The granule size and strength can be adjusted accordingly.

[0043] The resulting catalyst can be calcined in an inert atmosphere, such as a nitrogen stream, to produce amorphous chromium oxide. The calcination temperature is preferably 360°C or higher. From the standpoint of inhibiting crystallization, the calcination temperature is preferably from 380 to 460°C. The calcination time can be, for example, from 1 to 5 hours.

[0044] From the viewpoint of catalyst activity, the calcined catalyst preferably has a specific surface area of ​​170 m 2 / g or more, more preferably 180 m 2 / g or more, and even more preferably 200 m 2 / g or more. The upper limit of the specific surface area is generally preferably approximately 240 m 2 / g and more preferably approximately 220 m 2 / G.

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

[0046] Aluminosilicate catalysts can also be used as a complex oxide. Aluminosilicate catalysts are complex oxide catalysts containing silicon dioxide (SiO2) and aluminum oxide (Al2O3). For example, a catalyst having a silicon dioxide content of 20 to 90% by weight, especially 50 to 80% by weight, can be used, based on the total weight of silicon dioxide and aluminum oxide taken as 100% by weight.

[0047] In the present invention, a metal oxide catalyst such as the catalysts described above is fluorinated to obtain a fluorinated metal oxide catalyst. The fluorinated metal oxide catalyst has high activity, and fluorination also easily reduces catalyst degradation. Accordingly, even when the isomerization reaction is carried out for a long period of time, catalyst degradation can be slowed by adjusting the porosity. Therefore, the metal oxide catalyst is used in the form of a fluorinated metal oxide catalyst. The method for fluorinating the metal oxide catalyst is described later.

[0048] The catalyst of the present invention is prepared so as to have a large porosity, since this reduces catalyst degradation and can inhibit catalyst degradation even when the isomerization reaction is carried out for a long period of time. More specifically, the porosity of each metal oxide catalyst is such that the fluorinated chromium oxide has a porosity of 0.05 ml / g or more (especially from 0.075 to 1.5 ml / g), the fluorinated alumina has a porosity of 0.35 ml / g or more (especially from 0.40 to 2.0 ml / g), and the fluorinated aluminosilicate has a porosity of 0.50 ml / g or more (especially from 0.55 to 2.0 ml / g). When the porosity is smaller than this range, the pores where the active sites of the catalyst are present are covered with carbon, which is a by-product of the reaction, or the adhered carbon impairs gas diffusion in the pores, resulting in a decrease in the activity of the catalyst, that is, more likely to cause catalyst degradation.On the other hand, excessively high porosity complicates the catalyst production method and increases production costs.

[0049] The catalyst according to the present invention has increased porosity as described above. The porosity can be adjusted by the degree of fluorination of the catalyst, that is, by the content of fluorine atoms. Therefore, the content of fluorine atoms is preferably from 5.0 to 50% atoms, and more preferably from 10 to 25% atoms, based on the total amount of the catalyst in the present invention, taken as 100% atoms.

[0050] A method for fluorinating a metal oxide catalyst includes, for example, reacting a metal oxide with a fluorinating agent. Specifically, the metal oxide can be fluorinated, for example, by allowing the fluorinating agent to flow through the metal oxide. The metal oxide used in such fluorination can be the metal oxide of the fluorinated metal oxide described above.

[0051] The metal oxide catalyst before fluorination preferably has a large porosity, because this increases the porosity of the metal oxide catalyst after fluorination and improves the reaction conversion rate, and easily reduces catalyst degradation; meanwhile, catalyst degradation can be easily slowed down even when the isomerization reaction is carried out for a long period of time.More specifically, the preferred porosity of metal oxide catalysts before fluorination is, for example, chromium oxide having a porosity of 0.05 ml / g or more (especially 0.075 to 1.5 ml / g), aluminum oxide having a porosity of 0.45 ml / g or more (especially 0.50 to 2.5 ml / g), and aluminosilicate having a porosity of 0.40 ml / g or more (especially 0.50 to 2.0 ml / g). When the porosity is 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 adhered carbon is less likely to hinder gas diffusion in the pores. Accordingly, the activity of the catalyst can be maintained; that is, it is easy to inhibit the degradation of the catalyst, and the production method of the catalyst is also simple.

[0052] Examples of the fluorinating agent used for such fluorination include hydrofluorocarbons (R23: trifluoromethane, R32: difluoromethane, and R41: monofluoromethane), hydrochlorofluorocarbons (R22: chlorodifluoromethane and R21: dichloromonofluoromethane), chlorofluorocarbons (R13: chlorotrifluoromethane and R11: trichloromonofluoromethane), etc. Compared with hydrogen fluoride, these fluorinating agents generally increase the porosity of the fluorinated metal oxide catalyst, easily reduce catalyst degradation, and can easily inhibit catalyst degradation even when the isomerization reaction is carried out for a long period of time. These fluorinating agents can be used individually or in combination of two or more.

[0053] The fluorination conditions are not particularly limited. From the viewpoint of easily reducing catalyst degradation and easily inhibiting catalyst degradation, even when the isomerization reaction is carried out for a long period of time, the temperature is preferably 50 to 600°C (especially 100 to 500°C), the pressure is preferably 0 to 1000 kPa (especially 0.1 to 500 kPa), and the time is preferably 0.1 to 24 hours (especially 1 to 12 hours). Under these fluorination conditions, the fluorine atom content is preferably adjusted to fall within the above-described range.

[0054] The perfluoroalkyne compound to be obtained is, for example, a perfluoroalkyne represented by formula (1): (where the substituents R 1 -R 4 are the same or different and represent a fluorine atom or a perfluoroalkyl group).

[0055] Perfluoroalkyl group represented by substituents R 1 -R 4 in the formula (1) is not particularly limited, and examples include perfluoroalkyl groups having 1 to 6 (especially 1 to 4) carbon atoms. Specific examples include a trifluoromethyl group, a pentafluoroethyl group, and the like.

[0056] From the point of view of, for example, the degree of reaction conversion and the yield and selectivity of the resulting perfluoroalkyne compound, the substituents R 1 -R 4 in formula (1), all preferably represent a fluorine atom. Substituents R 1 -R 4 may be the same or different.

[0057] Thus, the perfluoroalkyne compound of formula (1) to be obtained includes, for example,

[0058] The perfluoroalkadiene compound as a substrate is preferably, for example, a perfluoroalkadiene represented by formula (2): (where the substituents R 1 -R 4 are the same or different and represent a fluorine atom or a perfluoroalkyl group).

[0059] Perfluoroalkyl group represented by substituents R 1 -R 4 in the formula (2) is not particularly limited, and examples include a perfluoroalkyl group having 1 to 6 (especially 1 to 4) carbon atoms. Specific examples include a trifluoromethyl group, a pentafluoroethyl group, and the like.

[0060] From the point of view of, for example, the degree of reaction conversion and the yield and selectivity of the resulting perfluoroalkyne compound, the substituents R 1 -R 4 in formula (2), preferably all represent a fluorine atom. Substituents R 1 -R 4 may be the same or different.

[0061] Examples of the perfluoroalkadiene of formula (2) that satisfies the above conditions include etc. These perfluoroalkadienes represented by formula (2) can be used singly or in combination of two or more.

[0062] The perfluoroalkadiene compound described above may be a known or commercially available product. The perfluoroalkadiene compound can also be synthesized by a conventional method, such as the method described in JP 2001-192345A.

[0063] [1-2] Catalyst and Method for Producing the Catalyst (No. 2) In the present invention, catalyst 2 for use in reacting (isomerizing) a perfluoroalkadiene compound to produce a perfluoroalkyne compound (which may be referred to as "isomerization reaction catalyst 2" hereinafter) contains a fluorinated metal oxide having a porosity of 0.35 ml / g or more. This catalyst satisfies the above requirement (D). Conventionally used isomerization reaction catalysts are not optimized in terms of porosity. It is unclear what porosity of the catalyst is usually used.The present invention utilizes fluorinated metal oxides having a certain porosity, and the porosity of the fluorinated metal oxides is increased to 0.35 ml / g or more, which results in an increased reaction conversion rate and easily reduces catalyst degradation; accordingly, catalyst degradation can be slowed down even when the isomerization reaction is carried out for a long period of time. Therefore, the use of the catalyst of the present invention can reduce the frequency of catalyst replacement and is therefore economical.

[0064] The catalyst of the present invention is not particularly limited. From the viewpoint of increasing the reaction conversion rate and easily reducing the degradation of the catalyst, as well as easily inhibiting the degradation of the catalyst even when isomerization is carried out for a long period of time, the catalyst preferably contains at least one element belonging to groups 3 to 14 of the periodic table of elements, more preferably at least one element belonging to groups 4 to 6 and groups 13 and 14 of the periodic table, and even more specifically, at least one element selected from the group consisting of chromium, titanium, silicon, aluminum, zirconium, and the like. The catalyst may contain only one, two, or more of the above-described metal elements.

[0065] From the viewpoint of having high activity in the isomerization reaction of a perfluoroalkadiene compound to a perfluoroalkyne compound, increasing the reaction conversion rate, and easily reducing catalyst degradation and easily inhibiting catalyst degradation even when the isomerization is carried out for a long period of time, the catalyst according to the present invention is particularly preferably a fluorinated alumina catalyst, a fluorinated aluminosilicate catalyst, a fluorinated zirconium oxide catalyst, or the like.

[0066] The titanium oxide catalyst used can be any catalyst containing titanium dioxide as the main component and may additionally contain one, two, or more other non-volatile substances, such as metal oxides, hydroxides, sulfates, nitrates, phosphates, and sulfides. The titanium oxide catalyst preferably contains titanium dioxide in an amount of 70% by weight or more.

[0067] The titanium dioxide is particularly preferably an antase titanium dioxide and preferably has a specific surface area of ​​5 to 100 m 2 / g and a porosity of 0.2 to 0.4 ml / g. The catalyst is preferably obtained in a spherical form. More specifically, commercially available catalysts such as CS-200, CS-300, and CS-950 (manufactured by Sakai Chemical Industry Co., Ltd.) can be preferably used.

[0068] Examples of the alumina catalyst and the aluminosilicate catalyst may include the catalysts described in Section [1-1] “Catalyst and Method for Producing the Catalyst (No. 1)” above.

[0069] The zirconium oxide catalyst is not particularly limited as long as the catalyst contains zirconium oxide as the main component. The catalyst may contain non-volatile substances such as other metal oxides, hydroxides, sulfates, nitrates, phosphates, and sulfides. The zirconium oxide catalyst preferably contains zirconium dioxide in an amount of 70% or more by weight.

[0070] In the present invention, a metal oxide catalyst such as the catalysts described above is fluorinated to produce a fluorinated metal oxide catalyst. The fluorinated metal oxide catalyst has high activity, and fluorination also easily reduces catalyst degradation. Accordingly, even when the isomerization reaction is carried out for a long period of time, catalyst degradation can be slowed by adjusting the porosity. Thus, the metal oxide catalyst is used in the form of a fluorinated metal oxide catalyst. The method for fluorinating the metal oxide catalyst is described below.

[0071] The catalyst according to the present invention preferably has an increased porosity, since this easily reduces the degradation of the catalyst; and the degradation of the catalyst can be easily slowed down even when the isomerization reaction is carried out for a long period of time. More specifically, the metal oxide catalyst after fluorination has a porosity of 0.35 ml / g or more, and preferably from 0.40 to 2.0 ml / g. The preferred porosity of the metal oxide catalysts, for example, is such that the fluorinated alumina has a porosity of 0.35 ml / g or more (especially from 0.40 to 2.0 ml / g), and the fluorinated aluminosilicate has a porosity of 0.50 ml / g (especially from 0.55 to 2.0 ml / g). When the porosity is in this range, the active sites of the catalyst are less likely to be covered with carbon, which is a by-product of the reaction; and the adhered carbon is less likely to interfere with gas diffusion in the pores.Accordingly, the activity of the catalyst can be maintained; that is, the degradation of the catalyst is easily slowed down, and the production method of the catalyst is also simple.

[0072] The fluorination degree (that is, the content of fluorine atoms) of the catalyst of the present invention, the fluorination method, the fluorinating agent, the fluorination conditions, and the like may be the same as the conditions described above in Section [1-1] “Catalyst and Method for Producing the Catalyst (No. 1)”.

[0073] The metal oxide catalyst before fluorination preferably has a large porosity, since this increases the porosity of the metal oxide catalyst after fluorination and increases the reaction conversion; and also easily reduces the degradation of the catalyst and easily slows down the degradation of the catalyst even when the isomerization reaction is carried out for a long period of time. More specifically, the metal oxide catalyst before fluorination preferably has a porosity of 0.45 ml / g or more, and more preferably from 0.50 to 2.5 ml / g. The preferred porosity of the metal oxide catalysts is, for example, such that alumina has a porosity of 0.45 ml / g or more (especially from 0.50 to 2.5 ml / g) and aluminosilicate has a porosity of 0.40 ml / g or more (especially from 0.50 to 2.0 ml / g).When porosity is within this range, the active sites of the catalyst are less likely to be covered by carbon, a byproduct of the reaction; and adhered carbon is less likely to impede gas diffusion within the pores. Consequently, catalyst activity can be maintained; that is, catalyst degradation is easily slowed, and the catalyst production process is also simple.

[0074] Examples of the perfluoroalkyne compound to be produced and the perfluoroalkadiene compound used as a substrate may be the same as the compounds described in Section [1-1] of “Catalyst and Catalyst Production Method (No. 1)” above.

[0075] 2. Method for producing a catalystThe method for producing a catalyst according to the present invention is a method for producing a catalyst for use in reacting a perfluoroalkadiene compound to produce a perfluoroalkyne compound, and the method comprises the following steps (E) or (F): (E) reacting a metal oxide with at least one compound selected from the group consisting of a hydrofluorocarbon, a hydrochlorofluorocarbon, and a chlorofluorocarbon to fluorinate the metal oxide; (F) fluorinating at least one metal oxide selected from the group consisting of chromium oxide having a porosity of 0.10 ml / g or more, aluminum oxide having a porosity of 0.45 ml / g or more, and aluminosilicate having a porosity of 0.50 ml / g or more.

[0076] [2-1] Catalyst Production Method (No. 3) In the present invention, a catalyst production method 3 for producing a catalyst for use in reacting (isomerizing) a perfluoroalkadiene compound to produce a perfluoroalkyne compound (which may be referred to hereinafter as the "isomerization reaction catalyst of production method 3") comprises reacting a metal oxide with at least one compound selected from the group consisting of a hydrofluorocarbon and a hydrochlorofluorocarbon to fluorinate the metal oxide. This catalyst satisfies the above-described requirement (E). Conventionally used isomerization reaction catalysts are not optimized in porosity. It is unclear what porosity of the catalyst is usually used.In the present invention, a metal oxide is fluorinated with a specific compound described above to ultimately adjust the porosity so that it falls within a predetermined range, increase the reaction conversion, and easily reduce catalyst degradation. Consequently, catalyst degradation can be slowed down even when the isomerization reaction is carried out for a long period of time. Therefore, the use of the catalyst according to the present invention can reduce the frequency of catalyst replacement and is therefore economical.

[0077] The metal oxide is not particularly limited. From the viewpoint of increasing the reaction conversion rate and easily reducing the catalyst degradation and easily inhibiting the catalyst degradation even when the isomerization is carried out for a long period of time, the metal of the metal oxide is preferably, for example, 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 and 14 of the periodic table; and more preferably, at least one component selected from the group consisting of chromium, titanium, silicon, aluminum, zirconium, and the like. The metal oxide may contain only one, or two, or more of the above-described metal elements.

[0078] The metal oxide particularly preferably includes chromium oxide catalysts, titanium oxide catalysts, alumina catalysts, aluminosilicate catalysts, zirconium oxide catalysts, or the like, since the fluorination of the metal oxide as described above increases the activity for the isomerization reaction of a perfluoroalkadiene compound to a perfluoroalkyne compound and increases the conversion rate of the reaction; and also easily reduces the degradation of the catalyst and easily slows down the degradation of the catalyst, even when the above-described isomerization reaction is carried out for a long period of time.

[0079] Examples of the chromium oxide catalyst, alumina catalyst, and aluminosilicate catalyst may be the same as those described in Section [1-1] of “Catalyst and Catalyst Production Method (No. 1)” above. Examples of the titanium oxide catalyst and zirconium oxide catalyst may be the same as those described in Section [1-2] of “Catalyst and Catalyst Production Method (No. 2)” above.

[0080] The metal oxide catalyst before fluorination, as described above, preferably has a large porosity. This increases the porosity of the metal oxide catalyst after fluorination and improves the reaction conversion rate; it also easily reduces catalyst degradation and easily slows down the catalyst degradation even when the isomerization reaction is carried out for a long period of time. More specifically, the metal oxide catalyst before fluorination preferably has a porosity of 0.45 ml / g or more, more preferably 0.50 to 2.5 ml / g. The preferred porosity of the metal oxide catalysts before fluorination is such a porosity that, for example, chromium oxide has a porosity of 0.05 ml / g or more (especially 0.075 to 1.5 ml / g), aluminum oxide has a porosity of 0.45 ml / g or more (especially 0.50 to 2.5 ml / g), and aluminosilicate has a porosity of 0.40 ml / g or more (especially 0.50 to 2.0 ml / g).When porosity is within this range, the active sites of the catalyst are less likely to be covered by carbon, a byproduct of the reaction; and the adhered carbon is less likely to impede gas diffusion within the pores. Consequently, catalyst activity can be maintained; that is, catalyst degradation is easily inhibited, and the catalyst production process is also simple.

[0081] In the present invention, a metal oxide catalyst such as the catalysts described above is fluorinated with a specific compound to produce a fluorinated metal oxide catalyst. The fluorinated metal oxide catalyst has high activity, and fluorination also easily reduces catalyst degradation. Accordingly, catalyst degradation can be slowed by adjusting porosity, even when the isomerization reaction is carried out for a long period of time. Therefore, the metal oxide catalyst is used in the form of a fluorinated metal oxide catalyst.

[0082] In the present invention, a method for fluorinating a metal oxide catalyst comprises reacting a metal oxide with a fluorinating agent. More specifically, the metal oxide can be fluorinated, for example, by passing the fluorinating agent through the metal oxide.

[0083] In the present invention, at least one compound selected from the group consisting of hydrofluorocarbons (R23: trifluoromethane, R32: difluoromethane, R41: monofluoromethane), hydrochlorofluorocarbons (R22: chlorodifluoromethane, R21: dichloromonofluoromethane) and chlorofluorocarbons (R13: chlorotrifluoromethane, R11: trichloromonofluoromethane) is used as a fluorinating agent in such fluorination. Compared with hydrogen fluoride, these fluorinating agents can increase the porosity of the fluorinated metal oxide catalyst and can reduce the degradation of the catalyst and slow down the degradation of the catalyst even when the isomerization reaction is carried out for a long period of time. These fluorinating agents can be used singly or in combination of two or more.

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

[0085] The catalyst obtained in this manner has high porosity. Considering the above, high porosity reduces catalyst degradation and can slow down catalyst degradation even when the isomerization reaction is carried out for a long period of time. Specifically, the metal oxide catalyst after fluorination preferably has a porosity of 0.35 ml / g or greater, more preferably 0.40 to 2.0 ml / g. The preferred porosity of the metal oxide catalysts is, for example, such that the fluorinated chromium oxide has a porosity of 0.05 ml / g or more (especially from 0.075 to 1.5 ml / g), the fluorinated aluminum oxide has a porosity of 0.35 ml / g or more (especially from 0.40 to 2.0 ml / g), and the fluorinated aluminosilicate has a porosity of 0.50 ml / g or more (especially from 0.55 to 2.0 ml / g).When porosity is within this range, the active sites of the catalyst are less likely to be covered by carbon, a byproduct of the reaction; and adhered carbon is less likely to impede gas diffusion within the pores. Consequently, catalyst activity can be maintained; that is, catalyst degradation is easily slowed, and the catalyst production process is also simple.

[0086] The catalyst obtained by this method has high porosity. The porosity can be adjusted by adjusting the degree of fluorination of the catalyst, that is, by adjusting the fluorine atom content. Therefore, the fluorine atom content of the resulting catalyst after fluorination is preferably from 5.0 to 50% atomic, more preferably from 10 to 25% atomic, based on 100% atomic, of the total amount of catalyst after fluorination.

[0087] Examples of the perfluoroalkyne compound to be produced and the perfluoroalkadiene compound used as a substrate may be the same as those described in Section [1-1] of “Catalyst and Method for Producing the Catalyst (No. 1)” above.

[0088] [2-2] Catalyst Production Method (No. 4) In the present invention, a catalyst production method 4 for producing a catalyst for use in reacting (isomerizing) a perfluoroalkadiene compound to produce a perfluoroalkyne compound (which may be referred to hereinafter as the "isomerization reaction catalyst of production method 4") comprises fluorinating at least one metal oxide selected from the group consisting of chromium oxide having a porosity of 0.10 ml / g or more before fluorinating the metal oxide, aluminum oxide having a porosity of 0.45 ml / g or more before fluorinating the metal oxide, and aluminosilicate having a porosity of 0.5 ml / g or more before fluorinating the metal oxide. This catalyst satisfies the above-described requirement (F). Conventionally used isomerization reaction catalysts are not optimized. in porosity. It is unclear what catalyst porosity is typically used.In the present invention, metal oxides having a certain porosity are fluorinated to increase the reaction conversion rate and easily reduce catalyst degradation; accordingly, catalyst degradation can be slowed down even when the isomerization reaction is carried out for a long period of time. Therefore, the use of the catalyst of the present invention can reduce the frequency of catalyst replacement and is therefore economical.

[0089] Examples of the chromium oxide catalyst, the alumina catalyst, and the aluminosilicate catalyst may be the same as the examples described above in Section [1-1] “Catalyst and Catalyst Production Method (No. 1)”.

[0090] The metal oxide catalyst before fluorination, as described above, preferably has a large porosity, since this increases the porosity of the metal oxide catalyst after fluorination and increases the reaction conversion; and can also reduce catalyst degradation and slow down the degradation of the catalyst even when the isomerization reaction is carried out for a long period of time. More specifically, the preferred porosity of the metal oxide catalyst before fluorination is such that chromium oxide has a porosity of 0.05 ml / g or more (especially from 0.075 to 1.5 ml / g), alumina has a porosity of 0.45 ml / g or more (especially from 0.50 to 2.5 ml / g), and aluminosilicate has a porosity of 0.40 ml / g or more (especially from 0.50 to 2.0 ml / g).When the porosity is smaller than this range, the pores containing the active catalyst sites become coated with carbon, a reaction byproduct, or the adhered carbon impedes gas diffusion into the pores, thereby reducing catalyst activity and increasing the likelihood of catalyst degradation. On the other hand, excessive porosity complicates catalyst production and increases production costs.

[0091] In the present invention, a metal oxide catalyst such as the catalysts described above is fluorinated to produce a fluorinated metal oxide catalyst. The fluorinated metal oxide catalyst has high activity, and fluorination also easily reduces catalyst degradation. Accordingly, catalyst degradation can be slowed by adjusting porosity, even when the isomerization reaction is carried out for a long period of time. Therefore, the metal oxide catalyst is used in the form of a fluorinated metal oxide catalyst.

[0092] The fluorination method, fluorinating agent, fluorination conditions, etc. may be the same as those described above in Section [1-1] “Catalyst and Catalyst Production Method (No. 1)”.

[0093] The catalyst obtained by this method has a large porosity. Taking into account the above, a large porosity reduces the degradation of the catalyst, and the degradation of the catalyst can be slowed down even when the isomerization reaction is carried out for a long period of time. More specifically, the preferred porosity of the metal oxide catalysts, for example, is such that fluorinated chromium oxide has a porosity of 0.05 ml / g or more (especially 0.075 to 1.5 ml / g), fluorinated alumina has a porosity of 0.35 ml / g (especially 0.40 to 2.0 ml / g), and fluorinated aluminosilicate has a porosity of 0.50 ml / g or more (especially 0.55 to 2.0 ml / g). When the porosity is in this range, the active sites of the catalyst are less likely to be covered with carbon, which is a by-product of the reaction; and the adhered carbon is less likely to interfere with gas diffusion in the pores.Accordingly, the activity of the catalyst can be maintained; that is, the degradation of the catalyst is easily slowed down, and the production method of the catalyst is also simple.

[0094] The catalyst obtained in this manner has high porosity. The porosity can be adjusted by adjusting the degree of fluorination of the catalyst, that is, by adjusting the fluorine atom content. Therefore, the fluorine atom content of the resulting catalyst after fluorination is preferably 5.0 to 50% by atom, more preferably 10 to 25% by atom, based on 100% by atom of the total amount of catalyst after fluorination.

[0095] Examples of the perfluoroalkyne compound to be produced and the perfluoroalkadiene compound used as a substrate "may be the same compounds as those described above in Section [1-1] of "Catalyst and Catalyst Production Method (No. 1)".

[0096] 3. Method for producing a perfluoroalkyne compound A method for producing a perfluoroalkyne compound according to the present invention comprises reacting a perfluoroalkadiene compound in the presence of a catalyst to produce a perfluoroalkyne compound and satisfies one of the following conditions (A) to (G): (A) the catalyst comprises at least one catalyst selected from the group consisting of catalysts containing a transition metal element and catalysts containing at least two elements that belong to groups 3 to 14 of the periodic table of the elements; (B) the catalyst comprises a catalyst containing at least one element that belongs to groups 3 to 14 of the periodic table, and the contact time between the catalyst and the perfluoroalkadiene compound represented by formula (2) is 30 seconds or less;(C) the catalyst comprises at least one catalyst selected from the group consisting of a fluorinated chromium oxide having a porosity of 0.08 ml / g or more, a fluorinated aluminum oxide having a porosity of 0.35 ml / g or more, and a fluorinated aluminosilicate having a porosity of 0.50 ml / g or more;(D) the catalyst comprises a fluorinated metal oxide having a porosity of 0.35 ml / g or more;(E) the catalyst comprises a metal oxide fluorinated by reacting at least one compound selected from the group consisting of a hydrofluorocarbon, a hydrochlorofluorocarbon, and a chlorofluorocarbon with the metal oxide;(F) the catalyst comprises one or more catalysts obtained by fluorinating at least one metal oxide selected from the group consisting of a chromium oxide having a porosity of 0.10 ml / g or more, an aluminum oxide having a porosity 0.45 ml / g or more, and an aluminosilicate having a porosity of 0.50 ml / g or more;and(G) at least a portion of the reaction of the perfluoroalkadiene compound from the beginning to the end of the reaction is carried out under conditions in which the reaction system has a water content of 30 ppm by weight or less based on the weight of the perfluoroalkadiene compound taken as 100% by weight;

[0097] Examples of the perfluoroalkyne compound and the perfluoroalkadiene compound may be the same compounds as those described above in Section [1-1] of “Catalyst and Catalyst Production Method (No. 1)”.

[0098] [3-1] Method for producing a perfluoroalkyne compound (No. 1) A first method for producing a perfluoroalkyne compound according to the present invention comprises reacting a perfluoroalkadiene compound in the presence of a catalyst to obtain a perfluoroalkyne compound, wherein 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 that belong to groups 3 to 14 of the periodic table. This production method satisfies the above-described requirement (A).

[0099] Publicly known methods for producing a perfluoroalkyne compound are limited to methods using a catalyst containing only one element belonging to Group 13 of the periodic table and not containing any transition metals; or a catalyst containing an alkali metal. According to the present invention, a catalyst containing a transition metal element or a catalyst containing at least two elements belonging to Groups 3 to 14 of the periodic table, none of which are conventionally used, is used to achieve a high reaction conversion and obtain a perfluoroalkyne compound with a high yield and high selectivity, thereby expanding the freedom of choice in the synthesis of the perfluoroalkyne compound.Thus, by using a catalyst, for example, a catalyst containing a transition metal element with high activity, or a catalyst containing at least two elements belonging to groups 3-14 of the periodic table, which has higher activity in the form of a mixed oxide, a perfluoroalkyne compound can be obtained with high selectivity at a high reaction conversion. Moreover, according to the present invention, unlike conventional methods, the fluoroalkene compound is less likely to be formed as a byproduct, as described below.

[0100] In the present invention, a catalyst containing a transition metal element or a catalyst containing at least two elements belonging to groups 3 to 14 of the periodic table is used as an isomerization reaction catalyst. Such a catalyst is not particularly limited. From the viewpoint of achieving a particularly high reaction conversion and producing a perfluoroalkyne compound with a high yield and high selectivity, the catalyst to be used is, for example, preferably 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 two elements belonging to groups 4 to 6 and groups 13 and 14 of the periodic table. The catalyst is more preferably a catalyst containing chromium, titanium, zirconium, or the like; a catalyst containing silicon and aluminum, or the like.

[0101] The isomerization reaction catalyst is preferably an optionally fluorinated chromium oxide catalyst (chromium oxide catalyst or fluorinated chromium oxide catalyst), an optionally fluorinated titanium oxide catalyst (titanium oxide catalyst or fluorinated titanium oxide catalyst), an optionally fluorinated zirconium oxide catalyst (zirconium oxide catalyst or fluorinated zirconium oxide catalyst) or an optionally fluorinated aluminosilicate catalyst (aluminosilicate catalyst or fluorinated aluminosilicate catalyst), since such catalysts exhibit high activity in the isomerization reaction of a perfluoroalkadiene compound to a perfluoroalkyne compound;and may also have high activity in the reaction of forming a perfluorocycloalkene compound depending on the reaction conditions, and the perfluorocycloalkene compound as well as the perfluoroalkyne compound are expected to be useful as a dry etching gas for semiconductors, as well as in various applications such as coolants, foaming agents and heat transfer agents.

[0102] Examples of the chromium oxide catalyst and the aluminosilicate catalyst can be the same catalysts as those described in Section [1-1] “Catalyst and Catalyst Production Method (No. 1)” above. Examples of the titanium oxide catalyst and the zirconium oxide catalyst can be the same catalysts as those described in Section [1-2] “Catalyst and Catalyst Production Method (No. 2)” above.

[0103] When fluorinating the catalyst, the fluorination degree (fluorine atom content), fluorination method, fluorinating agent and fluorination conditions may be the same as those described above in Section [1-1] “Catalyst and Catalyst Production Method (No. 1)”.

[0104] These isomerization reaction catalysts can be used individually or in combination of two or more.

[0105] The amount of the isomerization reaction catalyst described above may be a catalytic amount and is not particularly limited. From the viewpoint of achieving a particularly high reaction conversion and obtaining a perfluoroalkyne compound with a higher yield and higher selectivity, for example, the weight ratio of the catalyst to the feed rate of the perfluoroalkadiene compound per hour (W / F) is preferably from 0.1 to 200 g sec / cm3, and more preferably from 0.5 to 150 g sec / cm3. When using two or more isomerization reaction catalysts, it is preferable to adjust the total amount of the catalysts within the above range. The above W / F ratio specifies the amount of the catalyst, especially in the case of gas-phase reactions. Even when a liquid-phase reaction is used, the amount of fluoride used may be a catalytic amount and can be appropriately adjusted.

[0106] In the production method of the present invention, when carrying out the reaction of a perfluoroalkadiene compound, metallic nickel (particularly metallic nickel balls), activated carbon or the like can be used, in addition to the perfluoroalkadiene compound as a substrate and a catalyst for the isomerization reaction, in such an amount as to achieve a W / F ratio of 0.1 to 200 g⋅sec / cm3, particularly 0.5 to 150 g⋅sec / cm3, for the purpose of heat transfer and dilution of the catalyst concentration.

[0107] The production method of the present invention (in particular, reacting a perfluoroalkadiene compound) is preferably carried out in the gas phase, particularly in a gas-phase continuous flow process using a fixed-bed reactor; however, the method can also be carried out in the liquid phase. Carrying out the reaction in the gas phase can simplify the equipment, operation, etc., compared with carrying out the reaction in the liquid phase; and can also produce a perfluoroalkyne compound with a higher yield and higher selectivity than when carrying out the reaction in a batch system.

[0108] In the production method of the present invention, the reaction of the perfluoroalkadiene compound is preferably carried out by heating. More specifically, heating is preferably carried out after the perfluoroalkadiene compound as a substrate and the isomerization reaction catalyst are added to the reaction system. The heating temperature during such heating is preferably 170°C or more (for example, from 170 to 400°C), and more preferably from 180 to 280°C, in order to achieve a particularly high reaction conversion and obtain the perfluoroalkyne compound with high yield and high selectivity.

[0109] In the production method of the present invention, the contact time (reaction time) between the catalyst and the perfluoroalkadiene compound is not particularly limited. The contact time is preferably 1 to 100 seconds, and more preferably 2 to 30 seconds, in order to achieve a particularly high reaction conversion and obtain the perfluoroalkyne compound with high yield and high selectivity.

[0110] In the production method of the present invention, the reaction atmosphere for the perfluoroalkadiene compound is not particularly limited. For example, the reaction atmosphere is preferably an inert gas atmosphere (nitrogen atmosphere, argon atmosphere, etc.).

[0111] The production method of the present invention can produce not only a perfluoroalkyne compound but also a perfluorocycloalkene compound. Examples of the perfluorocycloalkene compound include perfluorocycloalkene compounds represented by formula (3):

[0112]

[0113] (where the substituents R 1 -R 4 have the meanings defined above). Detailed information on the perfluorocycloalkene compound is described below.

[0114] Thus, after completion of the reaction, purification is carried out according to the usual method if necessary; and as a result, a perfluoroalkyne compound can be obtained.

[0115] The perfluorocycloalkene compound produced as a by-product in the production method of the present invention can be purified by a conventional method if necessary; and then used as a substrate for producing a perfluoroalkyne compound. The method and conditions in this process can be the same as those described in Patent Document (PD) 2 (JP 2014-058488A). Preferred specific examples may be the same as those described in PD 2.

[0116] More specifically, when using a perfluorocycloalkene compound as a substrate, isomerization is carried out using an isomerization catalyst, resulting in a perfluoroalkyne compound. This step can be carried out in the gas phase, particularly in a continuous gas-phase flow process using a fixed-bed reactor. Alternatively, this step can also be carried out in a batch reaction.

[0117] The catalyst for the isomerization reaction is preferably sodium fluoride, which is easy to handle in the atmosphere due to its low hygroscopicity, has high activity, and ensures high selectivity. When sodium fluoride itself is used as a catalyst, it can be in powder form. Sodium fluoride in granular form is preferred for gas-phase continuous flow reactions. Sodium fluoride supported on a carrier such as alumina, porous aluminum fluoride, activated carbon, silica, or zeolite can also be used. Alternatively, sodium fluoride can be mixed with other components and then used.

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

[0119] The perfluorocycloalkene compound and perfluoroalkyne compound obtained as described above can be successfully used as etching gases for the formation of modern microstructures such as semiconductors and liquid crystals; and also in various fields of application, such as building blocks for organic synthesis. Detailed information on the building blocks for organic synthesis is described later.

[0120] [3-2] Method for Producing a Perfluoroalkyne Compound (No. 2)The second method for producing a perfluoroalkyne compound according to the present invention is a process comprising reacting a perfluoroalkadiene compound in the presence of a catalyst to obtain a perfluoroalkyne compound, 4 wherein the catalyst comprises at least one catalyst that belongs 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-described requirement (B).

[0121] Traditional methods for producing perfluoroalkyne compounds include methods using a catalyst containing only one element belonging to Group 13 of the periodic table and not containing any transition metals, such as aluminum halide or sodium fluoride; and methods using a catalyst containing an alkali metal. For example, in the case of using a catalyst containing only one element belonging to Group 13 of the periodic table and not containing any transition metals, there are only options in which the reaction time is long; that is, 32 seconds or longer.According to the present invention, by using a catalyst containing at least one element belonging to groups 3-14 of the periodic table and reducing the reaction time to 30 seconds or less, a high reaction conversion is achieved and the perfluoroalkyne compound is obtained with high yield and high selectivity, thereby expanding the freedom of choice in the synthesis of the perfluoroalkyne compound. According to this method, due to the short reaction time, this reaction can proceed economically. Moreover, according to the present invention, unlike conventional methods, the fluoroalkene compound is less likely to be produced as a byproduct, as described later.

[0122] In the present invention, a catalyst containing at least one element belonging to groups 3 to 14 of the periodic table is used as an isomerization reaction catalyst. Such a catalyst is not particularly limited. From the viewpoint of achieving a particularly high reaction conversion and producing a perfluoroalkyne compound with a higher yield and higher selectivity, catalysts containing a transition metal element and catalysts containing at least two elements belonging to groups 3 to 14 of the periodic table are preferable. Catalysts containing at least one transition metal element belonging to groups 4 to 6 of the periodic table and catalysts containing at least two elements belonging to groups 4 to 6 and groups 13 and 14 of the periodic table are more preferable. Catalysts containing chromium, titanium and zirconium, catalysts containing silicon and aluminum, and the like.are even more preferable.

[0123] The isomerization reaction catalyst is preferably an optionally fluorinated chromium oxide catalyst (chromium oxide catalyst or fluorinated chromium oxide catalyst), an optionally fluorinated titanium oxide catalyst (titanium oxide catalyst or fluorinated titanium oxide catalyst), an optionally fluorinated zirconium oxide catalyst (zirconium oxide catalyst or fluorinated zirconium oxide catalyst) or an optionally fluorinated aluminosilicate catalyst (aluminosilicate catalyst or fluorinated aluminosilicate catalyst), since such catalysts have high activity in the isomerization reaction of a perfluoroalkadiene compound to a perfluoroalkyne compound and may also have high activity in the reaction of forming a perfluorocycloalkene compound depending on the reaction conditions, wherein the perfluorocycloalkene compound as well as the perfluoroalkyne compound are expected toare useful as a dry etching gas for semiconductors, as well as in various applications such as coolants, blowing agents, heat transfer fluids, etc. In this embodiment, the optionally fluorinated alumina catalyst can also be used as a catalyst containing one element that belongs to group 13 of the periodic table.

[0124] Examples of the chromium oxide catalyst, the alumina catalyst, and the aluminosilicate catalyst may be the same as those described in Section [1-1] of “Catalyst and Catalyst Production Method (No. 1)” above. Examples of the titanium oxide catalyst and the zirconium oxide catalyst may be the same as those described in Section [1-2] of “Catalyst and Catalyst Production Method (No. 2)” above.

[0125] Such isomerization reaction catalysts can be used singly or in combination of two or more.

[0126] When the catalyst is fluorinated, the degree of fluorination (content of fluorine atoms), fluorination method, fluorinating agent and fluorination conditions may be the same as those described above in Section [1-1] “Catalyst and Catalyst Production Method (No. 1)”.

[0127] The amount of the isomerization reaction catalyst described above may be the same as the amount described above in Section [3-1] of “Producing Method of Perfluoroalkyne Compound (No. 1)”.

[0128] In the production method of the present invention, when the reaction of the perfluoroalkadiene compound is carried out, metallic nickel (particularly metallic nickel balls), activated carbon or the like can also be used, in addition to the perfluoroalkadiene compound as a substrate and a catalyst for the isomerization reaction, in such an amount as to obtain a W / F ratio of 0.1 to 200 g⋅sec / cm3, in particular, 0.5 to 150 g⋅sec / cm3, for the purpose of heat transfer and dilution of the catalyst concentration.

[0129] The production method of the present invention (in particular, introducing a perfluoroalkadiene compound into the reaction) can be carried out in the liquid phase, but it is preferably carried out in the gas phase, in particular, in a gas-phase continuous flow process using a fixed-bed reactor. This can simplify the equipment, operation, etc., compared with carrying out the reaction in the liquid phase, and can also produce a perfluoroalkyne compound with a higher yield and higher selectivity than carrying out the reaction in a batch system.

[0130] In the production method of the present invention, the reaction temperature and the reaction atmosphere when introducing the perfluoroalkadiene compound into the reaction may be the same as those described above in Section [3-1] Method for Producing a Perfluoroalkyne Compound (No. 1).

[0131] In the production method of the present invention, the contact time (reaction time) between the catalyst and the perfluoroalkadiene compound is 30 seconds or less, and preferably 25 seconds or less. When the contact time (reaction time) is more than 30 seconds, the yield of the perfluoroalkyne compound decreases. The lower limit of the contact time (reaction time) is not particularly limited, but is generally 1 second.

[0132] The production method of the present invention can produce not only a perfluoroalkyne compound but also a perfluorocycloalkene compound. Examples of the perfluorocycloalkene compound include perfluorocycloalkene compounds represented by formula (3):

[0133]

[0134] (where the substituents R 1 -R 4 have the meanings defined above). Detailed information on perfluorocycloalkene compounds is described later.

[0135] Thus, after completion of the reaction, purification can be carried out in a conventional manner if necessary; and as a result, a perfluoroalkyne compound can be obtained.

[0136] The perfluorocycloalkene compound obtained as a by-product in the production method of the present invention can be purified by a conventional method if necessary and then used as a substrate for producing a perfluoroalkyne compound. The method and conditions for producing the perfluoroalkyne compound in this process can be the same as those described above in Section [3-1] “Process for Producing a Perfluoroalkyne Compound (No. 1)”.

[0137] The perfluorocycloalkene compound and perfluoroalkyne compound obtained in this way can be successfully used as etching gases for the formation of modern microstructures such as semiconductors and liquid crystals, and also in various fields of application, such as building blocks for organic synthesis. Detailed information on the building block for organic synthesis will be provided later.

[0138] [3-3] Method for Producing a Perfluoroalkyne Compound (No. 3)A third method for producing a perfluoroalkyne compound according to the present invention is a process comprising reacting a perfluoroalkadiene compound in the presence of a catalyst to produce a perfluoroalkyne compound and satisfying one of the following conditions (C) to (F): (C) the catalyst comprises at least one catalyst selected from the group consisting of a fluorinated chromium oxide having a porosity of 0.08 ml / g or more, a fluorinated aluminum oxide having a porosity of 0.35 ml / g or more, and a fluorinated aluminosilicate having a porosity of 0.50 ml / g or more; (D) the catalyst comprises a fluorinated metal oxide having a porosity of 0.35 ml / g or more; (E) the catalyst comprises a metal oxide fluorinated by reacting the metal oxide with at least one compound, selected from the group consisting of a hydrofluorocarbon, a hydrochlorofluorocarbon, and a chlorofluorocarbon;and(F) the catalyst comprises one or more catalysts obtained by fluorinating at least one metal oxide selected from the group consisting of chromium oxide having a porosity of 0.10 ml / g or more, aluminum oxide having a porosity of 0.45 ml / g or more, and aluminosilicate having a porosity of 0.50 ml / g or more.;

[0139] Requirement (C) means that the isomerization reaction catalyst 1 of the present invention described in Section [1-1] “Catalyst and Catalyst Production Method (No. 1)” above is used. Requirement (D) means that the isomerization reaction catalyst 2 of the present invention described in Section [1-2] “Catalyst and Catalyst Production Method (No. 2)” above is used. Requirement (E) means that the catalyst obtained by the production method of the isomerization reaction catalyst 3 described in Section [2-1] “Catalyst Production Method (No. 3)” above is used. Requirement (F) means that the catalyst obtained by the production method of the isomerization reaction catalyst 4 described in Section [2-2] “Catalyst and Catalyst Production Method (No. 4)” above is used. The catalysts of the present invention may be used singly or in combination of two or more.

[0140] The present invention uses the above-described catalyst according to the invention, resulting in an increased reaction conversion and a reduced catalyst degradation. Consequently, even when the isomerization reaction is carried out for a long period of time, catalyst degradation can be slowed down. Therefore, the use of the catalyst according to the present invention can reduce the frequency of catalyst replacement and is therefore economical.

[0141] The amount of the catalyst of the present invention described above can be a catalytic amount and is not particularly limited. From the viewpoint of achieving a particularly high reaction conversion and easily reducing catalyst degradation and easily inhibiting catalyst degradation even when the isomerization reaction is carried out for a long period of time, the weight ratio of the catalyst to the feed rate of the perfluoroalkadiene compound per hour (W / F) is preferably from 0.1 to 200 g sec / cm3, and more preferably from 0.5 to 150 g sec / cm3. When using two or more catalysts for the isomerization reaction, it is preferable to adjust the total amount of the catalysts so that it is within the above range. The above W / F ratio accurately determines the amount of the catalyst, especially in the case of a gas-phase reaction. Even.When a liquid phase reaction is used, the amount of fluoride used may be a catalytic amount and may be adjusted accordingly.

[0142] In the production method of the present invention, metallic nickel (particularly metallic nickel balls), activated carbon or the like, in addition to the perfluoroalkadiene compound as a substrate and a catalyst for the isomerization reaction, can also be used in such an amount as to obtain a W / F ratio of 0.1 to 200 g⋅sec / cm3, particularly 0.5 to 150 g⋅sec / cm3, for the purpose of heat transfer and dilution of the catalyst concentration.

[0143] In the production method of the present invention, the isomerization reaction can be carried out in the liquid phase, but it is preferably carried out in the gas phase, especially in a gas-phase continuous flow process using a fixed-bed reactor. This can simplify the equipment and operation, etc., compared with carrying out the reaction in the liquid phase, and can also produce a perfluoroalkyne compound with a higher yield and higher selectivity than carrying out the reaction in a batch system. Moreover, this easily reduces catalyst degradation, and even when the isomerization reaction is carried out for a long period of time, catalyst degradation can be easily slowed down.

[0144] In the production method of the present invention, the isomerization reaction is preferably carried out with heating. More specifically, heating is preferably carried out after the perfluoroalkadiene compound as a substrate and the catalyst of the present invention are placed in the reaction system. The heating temperature during such heating is preferably 170°C or more (especially from 170 to 400°C) and more preferably from 180 to 280°C in order to achieve a particularly high reaction conversion, easily reduce catalyst degradation, and easily inhibit catalyst degradation, even when the isomerization reaction is carried out for a long period of time.

[0145] In the production method of the present invention, the reaction time for the isomerization reaction is not particularly limited. Since the production method of the present invention effectively reduces catalyst degradation and slows down the catalyst degradation even when the isomerization reaction is carried out for a long period of time, the present method is suitable for carrying out long-term reactions. The reaction time is preferably 10 to 200 hours, and more preferably 20 to 100 hours.

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

[0147] After completion of the reaction, purification can be carried out in a conventional manner if necessary, and as a result, a perfluoroalkyne compound can be obtained.

[0148] The perfluoroalkyne compound obtained as described above can be successfully used as an etching gas for the formation of modern microstructures such as semiconductors and liquid crystals, and also in various applications, such as building blocks for organic synthesis. Detailed information on the building block for organic synthesis will be provided below.

[0149] [3-4] Method for Producing a Perfluoroalkyne Compound (No. 4)The fourth method for producing a perfluoroalkyne compound according to the present invention is a method comprising reacting a perfluoroalkadiene compound in the presence of a catalyst to obtain a perfluoroalkyne compound, wherein at least a part of the reaction of the perfluoroalkadiene compound from the beginning to the end of the reaction is carried out under conditions in which the water content in the reaction system is 30 mass ppm or less based on the mass of the perfluoroalkadiene compound (taken as 100% by mass).

[0150] As a method for producing a perfluoroalkyne compound, a method is known that involves reacting and isomerizing a perfluoroalkadiene compound in the presence of a catalyst. However, no method is known that can reduce the degradation of the catalyst. According to the present invention, the reaction system has a water content of 30 ppm by mass or less based on the mass of the perfluoroalkadiene compound (100% by mass) in at least a part of the reaction from the beginning to the end of the reaction, so as to thereby reduce the degradation of the catalyst and maintain a high reaction conversion; accordingly, the degradation of the catalyst can also be slowed down even when the isomerization reaction is carried out for a long period of time.Furthermore, since the catalyst degradation rate also varies depending on the mass ratio of the catalyst to the feed rate of the perfluoroalkadiene compound per hour (W / F), catalyst degradation can be further slowed by increasing the W / F ratio; that is, by slowing the feed rate of the perfluoroalkadiene compound. Thus, using the production method according to the present invention, the frequency of catalyst replacement can be reduced, and the production method is therefore economical.

[0151] As described in more detail below, according to the present invention, the water content in the reaction system is controlled to a low level. This can effectively prevent water from covering the active sites of the catalyst and causing catalyst degradation. That is, regardless of the type of catalyst used, the method according to the present invention can prevent water from covering the active sites of the catalyst and can effectively reduce catalyst degradation. The isomerization reaction catalyst is not particularly limited.From the viewpoint of reducing the water content in the reaction system, thereby easily reducing the degradation of the catalyst and easily slowing down the degradation of the catalyst even when the isomerization reaction is carried out for a long period of time, the catalyst is preferably, for example, a catalyst containing at least one element belonging to groups 3 to 14 of the periodic table; more preferably, a catalyst containing at least one element belonging to groups 4 to 6 and groups 13 and 14 of the periodic table; and even more preferably, a catalyst containing at least one element selected from the group consisting of chromium, titanium, silicon and aluminum. The catalyst may contain only one, or two, or more of the metal elements described above.

[0152] From the viewpoint of having high activity in the isomerization reaction of a perfluoroalkadiene compound to a perfluoroalkyne compound, easily reducing the degradation of the catalyst by lowering the water content in the reaction system, and easily inhibiting the degradation of the catalyst even when the isomerization reaction is carried out for a long period of time, the isomerization reaction catalyst is particularly preferably an optionally fluorinated chromium oxide catalyst (chromium oxide catalyst or fluorinated chromium oxide catalyst), an optionally fluorinated titanium oxide catalyst (titanium oxide catalyst or fluorinated titanium oxide catalyst), an optionally fluorinated alumina catalyst (alumina catalyst or fluorinated alumina catalyst) or an optionally fluorinated aluminosilicate catalyst (aluminosilicate catalyst or fluorinated aluminosilicate catalyst).

[0153] Examples of the chromium oxide catalyst, the alumina catalyst, and the aluminosilicate catalyst may be the same as those described in Section [1-1] of “Catalyst and Catalyst Production Method (No. 1)” above. Examples of the titanium oxide catalyst and the zirconium oxide catalyst may be the same as those described in Section [1-2] of “Catalyst and Catalyst Production Method (No. 2)” above.

[0154] Such isomerization reaction catalysts may be used singly or in combination of two or more.

[0155] When the catalyst is fluorinated, the degree of fluorination (content of fluorine atoms), fluorination method, fluorinating agent and fluorination conditions may be the same as those described above in Section [1-1] “Catalyst and Catalyst Production Method (No. 1)”.

[0156] The amount of the isomerization reaction catalyst described above may be the same amount as that described above in Section [3-1] of “Producing Method of Perfluoroalkyne Compound (No. 1)”.

[0157] In the production method of the present invention, the isomerization reaction (perfluoroalkadiene compound reaction) can also be carried out using metallic nickel (particularly metallic nickel balls), activated carbon or the like, in addition to the perfluoroalkadiene compound as a substrate and an isomerization reaction catalyst, in such an amount as to obtain a W / F ratio of 0.1 to 200 g⋅sec / cm3, particularly 0.5 to 150 g⋅sec / cm3, for the purpose of heat transfer and dilution of the catalyst concentration.

[0158] In the production method of the present invention, at least a part of the isomerization reaction from the beginning to the end of the reaction (reaction of the perfluoroalkadiene compound) is carried out under conditions in which the reaction system has a water content of 30 ppm by mass or less, preferably 20 ppm by mass or less, based on the mass of the perfluoroalkadiene compound (taken as 100% by mass). The lower limit of the water content may be 1 ppm by mass. In the present invention, the water content in the reaction system can be controlled by, for example, feeding a perfluoroalkadiene compound having a specific water content, and the reaction atmosphere is an inert gas atmosphere, as described below.

[0159] In the present invention, the water content in the reaction system is 30 ppm by mass or less, as described above. The reaction system may have a water content of 30 ppm by mass or less at the beginning of the reaction, during the reaction, or at the end of the reaction. That is, it is sufficient if the water content in the reaction system is 30 ppm by mass or less in at least a part of the reaction from the beginning to the end of the reaction (at least at any time). From the viewpoint of more effectively inhibiting the degradation of the catalyst, the reaction system preferably has a water content of 30 ppm by mass or less (particularly 20 ppm by mass or less) at least at the beginning of the reaction. It is particularly preferable that the water content in the reaction system is maintained at 30 ppm by mass or less (particularly 20 ppm by mass or less) throughout the reaction from the beginning to the end of the reaction.

[0160] In the production method of the present invention, the reaction atmosphere in the isomerization reaction (perfluoroalkadiene compound reaction) is not particularly limited as long as the water content in the reaction system falls within the above range. The reaction atmosphere, for example, is preferably an inert gas atmosphere (nitrogen atmosphere, argon atmosphere, etc.). When the reaction atmosphere is an inert gas atmosphere, a water content of 30 ppm by mass or less in the reaction system can be expressed as the perfluoroalkadiene compound used as a substrate substantially having a water content of 30 ppm by mass or less. That is, when the reaction atmosphere is an inert gas atmosphere, the production method of the present invention can be described as a method comprising introducing a perfluoroalkadiene compound having a water content of 30 ppm by mass into the reaction. / million or less, in the presence of a catalyst to produce a perfluoroalkyne compound. In this case, the perfluoroalkyne compound may have a water content of 30 ppm by mass or less at the start of the reaction, more specifically, immediately before being brought into contact with the catalyst; the perfluoroalkyne compound in the reaction system may have a water content of 30 ppm by mass or less at some point during the reaction; or the perfluoroalkyne compound may have a water content of 30 ppm by mass or less immediately after the end of the reaction. That is, it is sufficient if the perfluoroalkyne compound has a water content of 30 ppm by mass or less in at least a part of the reaction from the start to the end of the reaction (at least at any time). The perfluoroalkyne compound preferably has a water content of 30 ppm by mass or less at the start of the reaction. It is particularly preferred that the perfluoroalkyne compound has a water content of 30 ppm by mass. / million or less throughout the reaction from the beginning to the end of the reaction.

[0161] In the production method of the present invention, the isomerization reaction (perfluoroalkadiene compound reaction) can be carried out in the liquid phase, but it is preferably carried out in the gas phase, in particular, in a gas-phase continuous flow process using a fixed-bed reactor. This can simplify the equipment, operation, etc., compared with carrying out the reaction in the liquid phase; and can also produce a perfluoroalkyne compound with a higher yield and higher selectivity than carrying out the reaction in a batch system. Moreover, reducing the water content in the reaction system makes it easier to reduce catalyst degradation, and the catalyst degradation can be easily slowed down even when the isomerization reaction is carried out for a long period of time.

[0162] In the production method of the present invention, the reaction temperature when introducing the perfluoroalkadiene compound into the reaction may be the same as described above in Section [3-1] “Production Method of Perfluoroalkyne Compound (No. 1)”.

[0163] In the production method of the present invention, the reaction time for the isomerization reaction (perfluoroalkadiene compound reaction) is not particularly limited. Since the production method of the present invention easily reduces catalyst degradation and slows down the catalyst degradation even when the isomerization reaction is carried out for a long period of time, the method is suitable for carrying out long-term reactions. The reaction time is preferably 10 to 200 hours, and more preferably 20 to 100 hours.

[0164] After completion of the reaction, purification can be carried out according to the usual method if necessary; and as a result, a perfluoroalkyne compound can be obtained.

[0165] The perfluoroalkyne compound obtained as described above can be successfully used as an etching gas for the formation of modern microstructures such as semiconductors and liquid crystals, as well as in various applications, such as building blocks for organic synthesis. Detailed information on the building block for organic synthesis is provided below.

[0166] 4. Perfluoroalkyne CompositionPerfluoroalkyne compounds can be produced as described above. However, using the production method described in Section [3-1] “Process for Producing a Perfluoroalkyne Compound (No. 1)” or Section [3-2] “Process for Producing a Perfluoroalkyne Compound (No. 2)” above, it is also likely that it can produce a product in the form of a perfluoroalkyne composition containing a perfluoroalkyne compound and a perfluorocycloalkene compound as described above. Using the production method described in Section [3-3] “Process for Producing a Perfluoroalkyne Compound (No. 3)” or Section [3-4] “Process for Producing a Perfluoroalkyne Compound (No. 4)” above can result in an exceptionally high selectivity with respect to the obtained perfluoroalkyne compound and can greatly reduce the content of other additional compounds in the product.

[0167] When a perfluoroalkyne compound is obtained in the form of a perfluoroalkyne composition, the perfluoroalkyne compound is preferably a perfluoroalkyne represented by formula (1): where the substituents R 1 -R 4 have the meanings defined above, and the perfluorocycloalkene compound is preferably a perfluorocycloalkene compound represented by formula (3):

[0168]

[0169] where are the substituents R 1 -R 4 have the meanings defined above. In the perfluoroalkyne composition of the present invention, the perfluoroalkyne compounds may be used individually or in combination of two or more.

[0170] Examples of perfluorocycloalkene compounds include the following compounds.

[0171] .

[0172] Perfluorocycloalkene compounds can be used singly or in combination of two or more.

[0173]

[0174] In addition to the perfluoroalkyne compounds and perfluorocycloalkene compounds mentioned above, the production method of the present invention can also produce, for example, a perfluoroalkene compound represented by formula (4A): where the substituents R1-R4 have the meanings defined above, and the fluoroalkene compound is represented by formula (4B): wherein the substituents Ri-R4 have the meanings defined above. However, according to the production method of the present invention, the fluoroalkene compound represented by formula (4B) is hardly obtained as a by-product.

[0175] Thus, the perfluoroalkyne composition of the present invention may also contain a perfluoroalkene compound represented by formula (4A) and a fluoroalkene compound represented by formula (4B). When the perfluoroalkene compound represented by formula (4A) is in the perfluoroalkyne composition of the present invention, its content 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 invention taken as 100 mol%. Further, when the fluoroalkene compound represented by formula (4B) is in the perfluoroalkyne composition of the present invention, its content is preferably 0 to 0.3 mol%, and more preferably 0.01 to 0.28 mol%. based on the total amount of the perfluoroalkyne composition according to the present invention, taken as 100 mol., since the fluoroalkene compound represented by formula (4B) is unlikely to be obtained as a by-product in the production method of the present invention.

[0176] According to the production method of the present invention, a perfluoroalkyne compound can be produced, in particular, with a high yield and high selectivity, as described above, even when it is produced as a perfluoroalkyne composition. Therefore, the content of components other than the perfluoroalkyne compound in the perfluoroalkyne composition can be reduced, and therefore, the effort required for purification to obtain the perfluoroalkyne compound can be reduced.

[0177] As with the perfluoroalkyne compound described separately above, the perfluoroalkyne composition of the present invention can also be successfully used in various fields of application, for example, as an etching gas used for the formation of advanced microstructures (e.g., semiconductors and liquid crystals) and a building block for organic synthesis. The term "building block for organic synthesis" means a substance that serves as a precursor for a compound having a highly reactive structure. For example, the perfluoroalkyne composition of the present invention can be converted into a substance that serves as a detergent or a fluorine-containing medical intermediate by reacting with a fluorine-containing organosilicon compound such as CF3Si(CH3)3 and introducing a fluoroalkyl group such as CF3.

[0178] Embodiments according to the present invention are described below; however, various changes in form and details may be made without departing from the spirit and scope of the claims. Examples

[0179] The distinctive features of the present invention are explained below with reference to examples. However, the present invention is not limited to these examples.

[0180] Example 1: Requirement (A) or (B)The following catalysts are used below in Example 1.Chromium oxide catalyst: Cr2O3Fluorinated chromium oxide catalyst (1): Cr2O3 is fluorinated by allowing hydrogen fluoride to pass through it at atmospheric pressure at a temperature of from 100 to 460°C for 3 to 4 hours.Titanium oxide catalyst: TiO2Fluorinated titanium oxide catalyst: TiO2 is fluorinated by allowing hydrogen fluoride to pass through it at atmospheric pressure at a temperature of from room temperature to 300°C for 3 to 4 hours.Fluorinated zirconium oxide catalyst: ZrO2 is fluorinated by allowing hydrogen fluoride to pass through it at atmospheric pressure at a temperature of from room temperature to 400°C for 3 to 4 hours.Aluminosilicate catalyst: SiO2 / Al2O3 80 / 10 to 60 / 20 (mass ratio).

[0181] Example 1-1: Fluorinated chromium oxide catalyst; W / F=30.0g⋅sec / cm3; 200°C; 23.1 secAs a catalyst, fluorinated chromium oxide catalyst (1) (chromium oxide fluorinated with hydrogen fluoride) was loaded into a metal tubular reactor. The reaction tube was heated to 200°C, and hexafluorobutadiene (CF2CF=CFCF2) was fed into the reaction tube until the W / F ratio reached 30.0g⋅sec / cm3 to ensure the reaction proceeded in gas phase continuous flow for 23.1 sec. One hour after the completion of the reaction, the gas exiting the reaction tube was analyzed by gas chromatography, which showed that the conversion rate was 100 mol%, and the selectivity of each component was as follows: 99.7 mol%. for 1,1,1,4,4,4-hexafluoro-2-butyne 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 (total amount of E-isomer and Z-isomer), 0.0947 mol.% for 1,1,1,2,4,4,4-heptafluoro-2-butene (the total amount of E-isomer and Z-isomer) and 0.0182 mol.% for all other by-products.

[0182] Example 1-2: Fluorinated chromium oxide catalyst; W / F=30.0g⋅sec / cm3; 250°C; 23.1 secThe reaction was carried out in the same manner as in Example 1-1, except that the reaction was carried out at a heating temperature of 250°C for 23.1 sec. One hour after the completion of the reaction, the gas outflowing from the reaction tube was analyzed by gas chromatography, which showed that the conversion degree was 100 mol%, and the selectivity of each component was as follows: 97.2 mol% for 1,1,1,4,4,4-hexafluoro-2-butyne (CF3C≡CCF3), 2.47 mol% for 1,2,3,3,4,4-hexafluoro-1-cyclobutene (c-C4F6), 0.0871 mol%. for 1,1,2,3,3,4,4,4-octafluoro-1-butene (CF2=CFCF2CF3) (total amount of E-isomer and Z-isomer), 0.262 mol.% for 1,1,1,2,4,4,4-heptafluoro-2-butene (CF3CF=CHCF3) (total amount of E-isomer and Z-isomer) and 0.0194 mol.% for all other by-products.

[0183] Example 1-3: Fluorinated chromium oxide catalyst; W / F=90.0 g⋅sec / cm3; 200°C; 69.3 secThe reaction was carried out in the same manner as in Example 1-1, except that the reaction was carried out at a W / F ratio of 90.0 g⋅sec / cm3 for 69.3 sec. One hour after completion of the reaction, the gas exiting the reaction tube was analyzed by gas chromatography, which showed that the conversion was 100 mol%, and the selectivity of each component was as follows: 99.7 mol% for 1,1,1,4,4,4-hexafluoro-2-butyne (CF3C≡CCF3), 0.118 mol% for 1,1,1,4,4,4-hexafluoro-2-butyne (CF3C≡CCF3), 0.118 mol% for 1,1,1,4,4,4-hexafluoro-2-butyne (CF3C≡CCF3). for 1,2,3,3,4,4-hexafluoro-1-cyclobutene (c-C4F6), 0.0254 mol.% for 1,1,2,3,3,4,4,4-octafluoro-1-butene (CF2=CFCF2CF3) (total amount of S-isomer and Z-isomer), 0.0911 mol.% for 1,1,1,2,4,4,4-heptafluoro-2-butene (CF3CF=CHCF3) (total amount of E-isomer and Z-isomer) and 0.0162 mol.% for all other by-products.

[0184] Example 1-4: Fluorinated titanium oxide catalyst; W / F=30.0 g⋅sec / cm3; 200°C; 32.5 secThe reaction was carried out in the same manner as in Example 1-1, except that the reaction was carried out for 32.5 sec using a fluorinated titanium oxide catalyst (titanium dioxide fluorinated with hydrogen fluoride) as the catalyst. One hour after the completion of the reaction, the gas exiting the reaction tube was analyzed by gas chromatography, which showed that the conversion was 93.0 mol%, and the selectivity for each component was as follows: 99.3 mol% for 1, 1,1,4,4,4-hexafluoro-2-butyne 0.354 mol% for 1,2,3,3,4,4-hexafluoro-1-cyclobutene (c-C4F6), 0.0595 mol% for 1,1,2,3,3,4,4,4-octafluoro-1-butene (total amount of E-isomer and Z-isomer), 0.0341 mol.% for 1,1,1,2,4,4,4-heptafluoro-2-butene (the total amount of E-isomer and Z-isomer) and 0.213 mol.% for all other by-products.

[0185] Example 1-5: Fluorinated titanium oxide catalyst; W / F=30.0 g⋅sec / cm3; 250°C; 32.5 secThe reaction was carried out in the same manner as in Example 1-1, except that the reaction was carried out at a heating temperature of 250°C for 32.5 sec using a fluorinated titanium oxide catalyst (titanium dioxide fluorinated with hydrogen fluoride) as a catalyst. One hour after the completion of the reaction, the gas exiting the reaction tube was analyzed by gas chromatography, which showed that the conversion was 99.9 mol%, and the selectivity for each component was as follows: 23.7 mol% for 1,1,1,4,4,4-hexafluoro-2-butyne 76.0 mol% for 1,2,3,3,4,4-hexafluoro-1-cyclobutene (c-C4F6), 0.00110 mol% for 1,1,2,3,3,4,4,4-octafluoro-1-butene (total amount of E-isomer and Z-isomer), 0.00421 mol.% for 1,1,1,2,4,4,4-heptafluoro-2-butene (the total amount of E-isomer and Z-isomer) and 0.295 mol.% for all other by-products.

[0186] Example 1-6: Fluorinated titanium oxide catalyst; W / F=30.0 g⋅sec / cm3; 300°C; 32.5 secThe reaction was carried out in the same manner as in Example 1-1, except that the reaction was carried out at a heating temperature of 300°C for 32.5 sec using a fluorinated titanium oxide catalyst (titanium dioxide fluorinated with hydrogen fluoride) as the catalyst. One hour after the completion of the reaction, the gas exiting the reaction tube was analyzed by gas chromatography, which showed that the conversion was 100 mol%, and the selectivity for each component was as follows: 44.5 mol% for 1,1,1,4,4,4-hexafluoro-2-butyne 55.1 mol% for 1,2,3,3,4,4-hexafluoro-1-cyclobutene (c-C4F6), 0.00601 mol% for 1,1,2,3,3,4,4,4-octafluoro-1-butene (total amount of E-isomer and Z-isomer), 0.00200 mol.% for 1,1,1,2,4,4,4-heptafluoro-2-butene (the total amount of E-isomer and Z-isomer) and 0.392 mol.% for all other by-products.

[0187] Example 1-7: Fluorinated zirconium oxide catalyst; W / F=30.0g⋅sec / cm3; 250°C; 14.9 secThe reaction was carried out in the same manner as in Example 1-1 except that the reaction was carried out at a heating temperature of 250°C for 14.9 sec using a fluorinated zirconium oxide catalyst (zirconia fluorinated with hydrogen fluoride) as a catalyst. One hour after completion of the reaction, the gas exiting the reaction tube was analyzed by gas chromatography, which showed that the conversion rate was 70.1 mol%, and the selectivity of each component was as follows: 4.18 mol% for 1,2,3,3,4,4-hexafluoro-1-cyclobutene (c-C4F6), 94.1 mol% for 1,2,3,3,4,4-hexafluoro-1-cyclobutene (c-C4F6). for 1,1,1,4,4,4-hexafluoro-2-butyne 0.00100 mol% for 1,1,2,3,3,4,4,4-octafluoro-1-butene (total amount of E-isomer and Z-isomer), 0.198 mol.% for 1,1,1,2,4,4,4-heptafluoro-2-butene (the total amount of E-isomer and Z-isomer) and 0.0760 mol.% for all other by-products.

[0188] Example 1-8: Fluorinated zirconium oxide catalyst; W / F=30.0 g⋅sec / cm3; 350°C; 14.9 secThe reaction was carried out in the same manner as in Example 1-1, except that the reaction was carried out at a heating temperature of 350°C for 14.9 sec using a fluorinated zirconium oxide catalyst (zirconia fluorinated with hydrogen fluoride) as a catalyst. One hour after the completion of the reaction, the gas exiting the reaction tube was analyzed by gas chromatography, which showed that the conversion was 99.5 mol%, and the selectivity for each component was as follows: 2.68 mol% for 1,1,1,4,4,4-hexafluoro-2-butyne 96.3 mol% for 1,2,3,3,4,4-hexafluoro-1-cyclobutene (c-C4F6), 0.0127 mol% for 1,1,2,3,3,4,4,4-octafluoro-1-butene (total amount of E-isomer and Z-isomer), 0.118 mol.% for 1,1,1,2,4,4,4-heptafluoro-2-butene (the total amount of E-isomer and Z-isomer) and 0.274 mol.% for all other by-products.

[0189] Example 1-9: Fluorinated zirconium oxide catalyst; W / F=15.0g⋅sec / cm3; 350°C; 7.5 secThe reaction was carried out in the same manner as in Example 1-1, except that the reaction was carried out at a heating temperature of 350°C with a W / F ratio of 15.0g⋅sec / cm3 for 7.5 sec, using a fluorinated zirconium oxide catalyst (zirconia fluorinated with hydrogen fluoride) as a catalyst. One hour after the completion of the reaction, the gas exiting the reaction tube was analyzed by gas chromatography, which showed that the conversion rate was 99.1 mol%, and the selectivity of each component was as follows: 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), 0.0163 mol.% for 1,1,2,3,3,4,4,4-octafluoro-1-butene (CF2=CFCF2CF3) (total amount of E-isomer and Z-isomer), 0.0851 mol.for 1,1,1,2,4,4,4-heptafluoro-2-butene (CF3CF=CHCF3) (total amount of E-isomer and Z-isomer) and 0.24 6 mol.% for all other by-products.

[0190] Table 1 shows the results of examples 1-1 to 1-9.

[0192] Example 1-10: Fluorinated chromium oxide catalyst; W / F=15.0 g⋅sec / cm3; 200°C; 16.2 secThe reaction was carried out in the same manner as in Example 1-1, except that the reaction was carried out at a W / F ratio of 15.0 g⋅sec / cm3 for 16.2 sec. One hour after the completion of the reaction, the gas exiting the reaction tube was analyzed by gas chromatography, which showed that the conversion was 100 mol%, and the selectivity for each component was as follows: 99.8 mol% for 1,1,1,4,4,4-hexafluoro-2-butyne 0.0991 mol% for 1,2,3,3,4,4-hexafluoro-1-cyclobutene (c-C4F6), below the detection limit (H / 0) for 1,1,2,3,3,4,4,4-octafluoro-1-butene (total amount of E-isomer and Z-isomer), 0.0850% mol. for 1,1,1,2,4,4,4-heptafluoro-2-butene- (the total amount of E-isomer and Z-isomer) and 0.0159 mol.% for all other by-products.

[0193] Example 1-11:_Chromium oxide_catalyst: W / F=30.0g⋅sec / cm3; 20°C; 25.1 secThe reaction was carried out in the same manner as in Example 1-1, except that the reaction was carried out at a heating temperature of 20°C for 25.1 sec using a chromium oxide catalyst as a catalyst. One hour after the completion of the reaction, the gas exiting the reaction tube was analyzed by gas chromatography, which showed that the conversion was 100 mol%, and the selectivity for each component was as follows: 99.8 mol% for 1,1,1,4,4,4-hexafluoro-2-butyne below the detection limit (L / D) for 1,2,3,3,4,4-hexafluoro-1-cyclobutene (c-C4F6), 0.0257 mol% for 1,1,2,3,3,4,4,4-octafluoro-1-butene (total amount of E-isomer and Z-isomer), 0.0511 mol.% for 1,1,1,2,4,4,4-heptafluoro-2-butene (the total amount of E-isomer and Z-isomer) and 0.0832 mol.% for all other by-products.

[0194] Example 1-12: Chromium oxide catalyst: W / F=14.0 g⋅sec / cm3; 20°C; 11.7 secThe reaction was carried out in the same manner as in Example 1, except that the reaction was carried out with a W / F ratio of 14.0 g⋅sec / cm3 under a heating temperature of 20°C for 11.7 sec using a chromium oxide catalyst as a catalyst. One hour after the completion of the reaction, the gas exiting the reaction tube was analyzed by gas chromatography, which showed that the conversion was 100 mol%, and the selectivity for each component was as follows: 99.8 mol% for 1,1,1,4,4,4-hexafluoro-2-butyne below the detection limit (L / D) for 1,2,3,3,4,4-hexafluoro-1-cyclobutene (c-C4F6), 0.0187 mol% for 1,1,2,3,3,4,4,4-octafluoro-1-butene (total amount of E-isomer and Z-isomer), 0.0544 mol.% for 1,1,1,2,4,4,4-heptafluoro-2-butene (the total amount of E-isomer and Z-isomer) and 0.0969 mol.% for all other by-products.

[0195] Example 1-13: Chromium oxide catalyst; W / F=30.0 g⋅sec / cm3; 50°C; 25.1 secThe reaction was carried out in the same manner as in Example 1-1, except that the reaction was carried out at a heating temperature of 50°C for 25.1 sec using a chromium oxide catalyst as the catalyst. One hour after the completion of the reaction, the gas exiting the reaction tube was analyzed by gas chromatography, which showed that the conversion was 100 mol%, and the selectivity for each component was as follows: 99.9 mol% for 1,1,1,4,4,4-hexafluoro-2-butyne below the detection limit (L / D) for 1,2,3,3,4,4-hexafluoro-1-cyclobutene (c-C4F6), 0.0201 mol% for 1,1,2,3,3,4,4,4-octafluoro-1-butene (total amount of E-isomer and Z-isomer), 0.0387 mol.% for 1,1,1,2,4,4,4-heptafluoro-2-butene (the total amount of E-isomer and Z-isomer) and 0.0012 mol.% for all other by-products.

[0196] Example 1-14: Chromium oxide catalyst; W / F=6.0 g⋅sec / cm3; 150°C; 5.0 secThe reaction was carried out in the same manner as in Example 1-1, except that the reaction was carried out with a W / F ratio of 6.0 g sec / cm3 at a heating temperature of 150°C for 5.0 sec using a chromium oxide catalyst as a catalyst. One hour after the completion of the reaction, the gas exiting the reaction tube was analyzed by gas chromatography, which showed that the conversion was 100 mol%, and the selectivity for each component was as follows: 99.8 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), 0.0274 mol% for 1,1,2,3,3,4,4,4-octafluoro-1-butene (total amount of E-isomer and Z-isomer), 0.0477 mol.% for 1,1,1,2,4,4,4-heptafluoro-2-butene (CF3CF=CHCF3) (total amount of E-isomer and Z-isomer) and 0.0818 mol.% for all other by-products.

[0197] Example 1-15: Chromium oxide catalyst; W / F=30.0 g⋅sec / cm3; 150°C; 25.1 secThe reaction was carried out in the same manner as in Example 1-1, except that the reaction was carried out at a heating temperature of 150°C for 25.1 sec using a chromium oxide catalyst as the catalyst. One hour after the completion of the reaction, the gas exiting the reaction tube was analyzed by gas chromatography, which showed that the conversion was 100 mol%, and the selectivity for each component was as follows: 99.8 mol% for 1,1,1,4,4,4-hexafluoro-2-butyne 0.00154 mol% for 1,2,3,3,4,4-hexafluoro-1-cyclobutene (c-C4F6), 0.0272 mol% for 1,1,2,3,3,4,4,4-octafluoro-1-butene (total amount of E-isomer and Z-isomer), 0.0364 mol.% for 1,1,1,2,4,4,4-heptafluoro-2-butene (the total amount of E-isomer and Z-isomer) and 0.125 mol.% for all other by-products.

[0198] Example 1-16: Chromium oxide catalyst; W / F=8.0g⋅sec / cm3; 200°C; 6.7 secThe reaction was carried out in the same manner as in Example 1-1 except that the reaction was carried out at a W / F ratio of 8.0g⋅sec / cm3 for 6.7 sec using a chromium oxide catalyst as the catalyst. One hour after completion of the reaction, the gas exiting the reaction tube was analyzed by gas chromatography, which showed that the conversion was 99.9 mol%, and the selectivity of each component was as follows: 99.6 mol% for 1,1,1,4,4,4-hexafluoro-2-butyne (CF3C=CCF3), 0.00311 mol% for 1,1,1,4,4,4-hexafluoro-2-butyne (CF3C=CCF3), 0.00511 mol%. for 1,2,3,3,4,4-hexafluoro-1-cyclobutene (c-C4F6), below the detection limit (L / D) for 1,1,2,3,3,4,4,4-octafluoro-1-butene (total amount of E-isomer and Z-isomer), 0.00111 mol.% for 1,1,1,2,4,4,4-heptafluoro-2-butene (the total amount of E-isomer and Z-isomer) and 0.416 mol.% for all other by-products.

[0199] Example 1-17: Chromium oxide catalyst; W / F=16.0 g⋅sec / cm3; 200°C; 13.3 secThe reaction was carried out in the same manner as in Example 1-1, except that the reaction was carried out at a W / F ratio of 16.0 g⋅sec / cm3 for 13.3 sec using a chromium oxide catalyst as the catalyst. One hour after the completion of the reaction, the gas exiting the reaction tube was analyzed by gas chromatography, which showed that the conversion was 100 mol%, and the selectivity for each component was as follows: 99.9 mol% for 1,1,1,4,4,4-hexafluoro-2-butyne 0.00311 mol% for 1,2,3,3,4,4-hexafluoro-1-cyclobutene (c-C4F6), below the detection limit (L / D) for 1,1,2,3,3,4,4,4-octafluoro-1-butene (total amount of E-isomer and Z-isomer), 0.00101 mol.% for 1,1,1,2,4,4,4-heptafluoro-2-butene (the total amount of E-isomer and Z-isomer) and 0.0959 mol.% for all other by-products.

[0200] Example 1-18:_Titanium oxide catalyst; W / F=10.0 g⋅sec / cm3; 200°C; 11.1 secThe reaction was carried out in the same manner as in Example 1-1, except that the reaction was carried out at a W / F ratio of 10.0 g⋅sec / cm3 for 11.1 sec using a titanium oxide catalyst as the catalyst. One hour after completion of the reaction, the gas exiting the reaction tube was analyzed by gas chromatography, which showed that the conversion was 99.0 mol%, and the selectivity for each component was as follows: 99.4 mol% for 1,1,1,4,4,4-hexafluoro-2-butyne 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 (total amount of E-isomer and Z-isomer), 0.0341 mol.% for 1,1,1,2,4,4,4-heptafluoro-2-butene (the total amount of E-isomer and Z-isomer) and 0.213 mol.% for all other by-products.

[0201] Example 1-19: Titanium oxide catalyst; W / F=14.0 g⋅sec / cm3; 200°C; 15.5 secThe reaction was carried out in the same manner as in Example 1-1, except that the reaction was carried out at a W / F ratio of 14.0 g⋅sec / cm3 for 15.5 sec using a titanium oxide catalyst as the catalyst. One hour after the completion of the reaction, the gas exiting the reaction tube was analyzed by gas chromatography, which showed that the conversion was 99.0 mol%, and the selectivity for each component was as follows: 99.3 mol% for 1,1,1,4,4,4-hexafluoro-2-butyne 0.362 mol% for 1,2,3,3,4,4-hexafluoro-1-cyclobutene (c-C4F6), 0.0587 mol% for 1,1,2,3,3,4,4,4-octafluoro-1-butene (total amount of E-isomer and Z-isomer), 0.0321 mol.% for 1,1,1,2,4,4,4-heptafluoro-2-butene (the total amount of E-isomer and Z-isomer) and 0.247 mol.% for all other by-products.

[0202] Example 1-20: Aluminosilicate catalyst; W / F=7.5g⋅sec / cm3; 20°C; 14.9 secThe reaction was carried out in the same manner as in Example 1-1, except that the reaction was carried out with a W / F ratio of 7.5g⋅sec / cm3 under a heating temperature of 20°C for 14.9 sec using an aluminosilicate catalyst as a catalyst. One hour after the completion of the reaction, the gas exiting the reaction tube was analyzed by gas chromatography, which showed that the conversion was 100 mol%, and the selectivity for each component was as follows: 99.4 mol% for 1,1,1,4,4,4-hexafluoro-2-butyne below the detection limit (L / D) for 1,2,3,3,4,4-hexafluoro-1-cyclobutene (c-C4F6), below the detection limit (L / D) for 1,1,2,3,3,4,4,4-octafluoro-1-butene (total amount of E-isomer and Z-isomer), 0.0909 mol.% for 1,1,1,2,4,4,4-heptafluoro-2-butene (the total amount of E-isomer and Z-isomer) and 0.504 mol.% for all other by-products.

[0203] Example 1-21: Aluminosilicate catalyst; W / F=15.0 g⋅sec / cm3; 20°C; 29.9 secThe reaction was carried out in the same manner as in Example 1-1, except that the reaction was carried out with a W / F ratio of 15.0 g⋅sec / cm3 under a heating temperature of 20°C for 29.9 sec using an aluminosilicate catalyst as a catalyst. One hour after the completion of the reaction, the gas exiting the reaction tube was analyzed by gas chromatography, which showed that the conversion was 100 mol%, and the selectivity for each component was as follows: 99.9 mol% for 1,1,1,4,4,4-hexafluoro-2-butyne below the detection limit (L / D) for 1,2,3,3,4,4-hexafluoro-1-cyclobutene (c-C4F6), 0.00688 mol% for 1,1,2,3,3,4,4,4-octafluoro-1-butene (total amount of E-isomer and Z-isomer), 0.0555% mol. for 1,1,1,2,4,4,4-heptafluoro-2-butene (the total amount of E-isomer and Z-isomer) and 0.0374 mol.% for all other by-products.

[0204] Example 1-22: Aluminosilicate catalyst; W / F=30.0 g⋅sec / cm3; 20°C; 59.8 secThe reaction was carried out in the same manner as in Example 1-1, except that the reaction was carried out at a heating temperature of 20°C for 59.8 sec using an aluminosilicate catalyst as the catalyst. One hour after the completion of the reaction, the gas exiting the reaction tube was analyzed by gas chromatography, which showed that the conversion was 100 mol%, and the selectivity for each component was as follows: 99.8 mol% for 1,1,1,4,4,4-hexafluoro-2-butyne below the detection limit (L / D) for 1,2,3,3,4,4-hexafluoro-1-cyclobutene (c-C4F6), below the detection limit (L / D) for 1,1,2,3,3,4,4,4-octafluoro-1-butene (total amount of E-isomer and Z-isomer), 0.0804 mol.% for 1,1,1,2,4,4,4-heptafluoro-2-butene (the total amount of E-isomer and Z-isomer) and 0.161 mol.% for all other by-products.

[0205] Example 1-23: Aluminosilicate catalyst; W / F=4.0 g⋅sec / cm3; 100°C; 8.0 secThe reaction was carried out in the same manner as in Example 1, except that the reaction was carried out with a W / F ratio of 4.0 g⋅sec / cm3 under a heating temperature of 100°C for 8.0 sec using an aluminosilicate catalyst as a catalyst. One hour after the completion of the reaction, the gas exiting the reaction tube was analyzed by gas chromatography, which showed that the conversion was 100 mol%, and the selectivity for each component was as follows: 99.4 mol% for 1,1,1,4,4,4-hexafluoro-2-butyne 0.00121 mol% for 1,2,3,3,4,4-hexafluoro-1-cyclobutene (c-C4F6), below the detection limit (L / D) for 1,1,2,3,3,4,4,4-octafluoro-1-butene (total amount of E-isomer and Z-isomer), 0.0909 mol.% for 1,1,1,2,4,4,4-heptafluoro-2-butene

[0206] Example 1-24: Aluminosilicate catalyst; W / F=4.0 g⋅sec / cm3; 200°C; 8.0 secThe reaction was carried out in the same manner as in Example 1-1, except that the reaction was carried out at a W / F ratio of 4.0 g⋅sec / cm3 for 8.0 sec using an aluminosilicate catalyst as the catalyst. One hour after the completion of the reaction, the gas exiting the reaction tube was analyzed by gas chromatography, which showed that the conversion was 100 mol%, and the selectivity for each component was as follows: 99.5 mol% for 1,1,1,4,4,4-hexafluoro-2-butyne 0.0670 mol% for 1,2,3,3,4,4-hexafluoro-1-cyclobutene (c-C4F6), below the detection limit (L / D) for 1,1,2,3,3,4,4,4-octafluoro-1-butene (total amount of E-isomer and Z-isomer), 0.0101 mol.% for 1,1,1,2,4,4,4-heptafluoro-2-butene (the total amount of E-isomer and Z-isomer) and 0.467 mol.% for all other by-products.

[0207] Example 1-25: Aluminosilicate catalyst; W / F=8.0 g⋅sec / cm3; 200°C; 16.0 secThe reaction proceeded in the same manner as in Example 1-1, except that the reaction was carried out at a W / F ratio of 8.0 g⋅sec / cm3 for 16.0 sec using an aluminosilicate catalyst as the catalyst. One hour after the completion of the reaction, the gas exiting the reaction tube was analyzed by gas chromatography, which showed that the conversion was 100 mol%, and the selectivity for each component was as follows: 99.5 mol% for 1,1,1,4,4,4-hexafluoro-2-butyne 0.0611 mol% for 1,2,3,3,4,4-hexafluoro-1-cyclobutene (c-C4F6), below the detection limit (L / D) for 1,1,2,3,3,4,4,4-octafluoro-1-butene (total amount of E-isomer and Z-isomer), 0.00921 mol.% for 1,1,1,2,4,4,4-heptafluoro-2-butene (the total amount of E-isomer and Z-isomer) and 0.480 mol.% for all other by-products.

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

[0211] Example 2: Requirements (C) to (F)The following catalysts were used in Example 2 below.Fluorinated chromium oxide catalyst (1): chromium oxide fluorinated with hydrogen fluoride; porosity, 0.10 ml / g; chromium oxide (Cr2O3, porosity, 0.15 ml / g) was fluorinated by allowing hydrogen fluoride to pass through it at atmospheric pressure at a temperature of from 100 to 400°C for 6 hours.Fluorinated chromium oxide catalyst (2): chromium oxide fluorinated with chlorodifluoromethane (R22); porosity, 0.13 ml / g; Chromium oxide (Cr2O3, porosity 0.15 ml / g) is fluorinated by allowing chlorodifluoromethane (R22) to pass through it at atmospheric pressure at a temperature of 100 to 500°C for 6 hours. Fluorinated aluminosilicate catalyst (1): aluminosilicate fluorinated with hydrogen fluoride; porosity 0.55 ml / g; aluminosilicate (porosity 0.70 ml / g) is fluorinated by allowing hydrogen fluoride to pass through it at atmospheric pressure at a temperature of 100 to 400°C for 6 hours.Fluorinated aluminosilicate catalyst (2): aluminosilicate fluorinated with chlorodifluoromethane (R22); porosity 0.69 ml / g; aluminosilicate (porosity 0.70 ml / g) is fluorinated by allowing chlorodifluoromethane (R22) to pass through it at atmospheric pressure at a temperature of 100 to 500°C for 6 hours.

[0212] All fluorinated alumina catalysts are prepared by fluorinating a given alumina by allowing hydrogen fluoride to pass through it at atmospheric pressure at a temperature of 100 to 400°C for 6 hours. Table 4 shows the detailed data for the fluorinated alumina catalysts.

[0214] Example 2-1: Chromium oxide catalyst fluorinated with R22; Porosity 0.13 ml / g As a catalyst, fluorinated chromium oxide catalyst (2) (chromium oxide fluorinated with chlorodifluoromethane (R22)) was loaded into a metal tubular reactor. The reaction tube was heated to 200°C and hexafluorobutadiene fed into the reaction tube until a W / F ratio of 8 g⋅sec / cm3 is achieved to ensure the reaction proceeds in a gas-phase continuous flow process. After a specified period of time, the gas exiting the reaction tube is analyzed using gas chromatography. The results show a catalyst degradation rate of -0.12% / hour. The catalyst degradation rate is represented by the slope of the graph obtained by plotting reaction time on the horizontal axis and the degree of conversion on the vertical axis. Table 5 presents the results.

[0216] Example 2-2: Aluminosilicate Catalyst Fluorinated with R22; Porosity 0.69 mL / gThe reaction proceeded in the same manner as Example 2-1 except that the fluorinated aluminosilicate catalyst (2) (aluminosilicate fluorinated with chlorodifluoromethane (R22)) was used as the catalyst instead of the fluorinated chromium oxide catalyst (2). After a predetermined period of time, the gas exiting the reaction tube was analyzed by gas chromatography. The results showed that the catalyst degradation rate was -0.0014% / hour. The catalyst degradation rate was represented by the slope of a graph obtained by plotting the reaction time on the horizontal axis and the conversion on the vertical axis. The results are shown in Table 6.

[0218] Example 2-3: Fluorinated alumina catalyst; Porosity 1.33 ml / gThe reaction proceeded 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 chromium oxide catalyst (2). After a predetermined period of time, the gas exiting the reaction tube was analyzed by gas chromatography. The results showed that the catalyst degradation rate was -0.025% / hour. The catalyst degradation rate is represented by the slope of a graph obtained by plotting the reaction time on the horizontal axis and the conversion on the vertical axis. The results are shown in Table 7.

[0219]

[0220] Example 2-4: Fluorinated alumina catalyst; Porosity 0.4 3 mL / gThe reaction proceeded 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 chromium oxide catalyst (2). After a predetermined period of time, the gas exiting the reaction tube was analyzed by gas chromatography. The results showed that the catalyst degradation rate was -0.026% / hour. The catalyst degradation rate was represented by the slope of a graph obtained by plotting the reaction time on the horizontal axis and the conversion on the vertical axis. The results were shown in Table 8.

[0221]

[0222] Comparative Example 2-1: Fluorinated Alumina Catalyst; Porosity 0.22 mL / gThe reaction proceeded in the same manner as Example 2-1, except that the fluorinated alumina catalyst (3) was used as the catalyst instead of the fluorinated chromium oxide catalyst (2). After a predetermined period of time, the gas exiting the reaction tube was analyzed by gas chromatography. The results showed that the catalyst degradation rate was -0.65% / hour. The catalyst degradation rate is represented by the slope of a graph obtained by plotting the reaction time on the horizontal axis and the conversion on the vertical axis. The results are shown in Table 9.

[0224] Example 2-5: Fluorinated alumina catalyst; Porosity 0.39 ml / gThe reaction proceeded 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 chromium oxide catalyst (2). After a predetermined period of time, the gas exiting the reaction tube was analyzed by gas chromatography. The results showed that the catalyst degradation rate was -0.29% / hour. The catalyst degradation rate is represented by the slope of the graph obtained by plotting the reaction time on the horizontal axis and the conversion on the vertical axis. The results are shown in Table 10.

[0226] Comparative Example 2-2: Fluorinated Alumina Catalyst; Porosity 0.23 mL / gThe reaction proceeded in the same manner as Example 2-1, except that the fluorinated alumina catalyst (5) was used as the catalyst instead of the fluorinated chromium oxide catalyst (2). After a predetermined period of time, the gas exiting the reaction tube was analyzed by gas chromatography. The results showed that the catalyst degradation rate was -0.67% / hour. The catalyst degradation rate is represented by the slope of a graph obtained by plotting the reaction time on the horizontal axis and the conversion on the vertical axis. The results are shown in Table 11.

[0228] Based on the results shown in Tables 7-11 above, FIG. 1 shows the relationship between the elapsed time (contact time) and the conversion rate, FIG. 2 shows the relationship between the porosity before fluorination and the degradation rate, and FIG. 3 shows the relationship between the porosity after fluorination and the degradation rate.

[0229] Example 3: Requirement (G)In Example 3 below, a chromium oxide catalyst (Cr2O3) or an alumina catalyst (Al2O3) is used as the catalyst.

[0230] The water content of hexafluorobutadiene is adjusted by adding water or by dehydrating it with molecular sieves to achieve the desired water content. Water content is measured using the Karl-Fischer method.

[0231] Example 3-1: Chromium oxide catalyst; Water content 20 ppm. The metal tube reactor is filled with nitrogen to create a nitrogen atmosphere, and then the chromium oxide catalyst is fed as a catalyst. The reaction tube is heated to 200°C and hexafluorobutadiene is fed into the reaction tube until a W / F ratio of 8 g⋅sec / cm3 is achieved to ensure the reaction proceeds in a gas-phase continuous flow process. The water content of hexafluorobutadiene at the beginning of the reaction is 20 ppm by mass, and the water content in the reaction system from the beginning to the end of the reaction is adjusted to 20 ppm. After a specified period of time, the gas exiting the reaction tube is analyzed by gas chromatography. The results show that the catalyst degradation rate is 0.12% / hour. The catalyst degradation rate is represented by the slope of the graph obtained by plotting the reaction time on the horizontal axis and the degree of conversion on the vertical axis. The results are presented in Table 12.

[0233] Example 3-2: Chromium Oxide Catalyst; Water Content 2 ppmThe reaction proceeded in the same manner as Example 3-1, except that the water content in the reaction system from the beginning to the end of the reaction was adjusted to 2 ppm by using hexafluorobutadiene with a water content of 2 ppm by mass at the beginning of the reaction instead of hexafluorobutadiene with a water content of 20 ppm by mass at the beginning of the reaction. After a predetermined period of time, the gas exiting the reaction tube was analyzed by gas chromatography. The results showed that the catalyst degradation rate was -0.12% / hour. The catalyst degradation rate was represented by the slope of a graph obtained by plotting the reaction time on the horizontal axis and the conversion on the vertical axis. The results were shown in Table 13.

[0235] Example 3-3: Alumina catalyst; Water content 20 ppmThe reaction proceeded in the same manner as in Example 3-1, except that an alumina catalyst was used instead of a chromium oxide catalyst. After a predetermined period of time, the gas exiting the reaction tube was analyzed by gas chromatography. The results showed that the catalyst degradation rate was -0.0302% / hour. The catalyst degradation rate is represented by the slope of a graph obtained by plotting the reaction time on the horizontal axis and the conversion on the vertical axis. The results are presented in Table 14.

[0236]

[0237] Example 3-4: Alumina Catalyst; Water Content 2 ppmThe reaction proceeded the same as in Example 3-1, except that an alumina catalyst was used instead of a chromium oxide catalyst, and that the water content in the reaction system from the beginning to the end of the reaction was adjusted to 2 ppm by using hexafluorobutadiene with a water content of 2 ppm by mass at the beginning of the reaction instead of hexafluorobutadiene with a water content of 20 ppm by mass at the beginning of the reaction. After a predetermined period of time, the gas exiting the reaction tube was analyzed by gas chromatography. The results showed that the catalyst degradation rate was 0.08% / hour. The catalyst degradation rate was represented by the slope of a graph obtained by plotting the reaction time on the horizontal axis and the conversion on the vertical axis. The results are shown in Table 15.

[0238]

Claims

1. A method for producing a perfluoroalkyne compound, which comprises reacting a perfluoroalkadiene compound in the presence of a catalyst to obtain the perfluoroalkyne compound and satisfying the following condition (G): (G) at least a part of the reaction of the perfluoroalkadiene compound from the beginning to the end of the reaction is carried out under conditions in which the water content in the reaction system is 30 ppm by mass or less based on the mass of the perfluoroalkadiene compound taken as 100% by mass. wherein the catalyst comprises at least one element that belongs to groups 4-6 and groups 13-14 of the periodic table.

2. The production method according to claim 1, wherein the perfluoroalkyne compound is represented by formula (1): CR 1 2R 2 -C≡C-CR 3 R 4 2(1) where the substituents R 1 -R 4are the same or different and represent a fluorine atom or a perfluoroalkyl group.

3. The production method according to claim 1 or 2, wherein the perfluoroalkadiene compound is represented by formula (2): CR 1 2=CR 2 -CR 3 =CR 4 2(2) where the substituents R 1 -R 4 are the same or different and represent a fluorine atom or a perfluoroalkyl group.

4. The production method according to any one of claims 1-3, wherein the reaction of the perfluoroalkadiene compound is carried out in the gas phase.

5. The production method according to any one of claims 1 to 4, wherein the reaction of the perfluoroalkadiene compound is carried out at a temperature of 170°C or higher.

6. The production method according to any one of claims 1 to 5, wherein the reaction of the perfluoroalkadiene compound produces a perfluorocycloalkene compound in addition to the perfluoroalkyne compound.

7. The production method according to claim 6, wherein the perfluorocycloalkene compound is represented by formula (3): where the substituents R 1 -R 4 have the meanings defined above.

8. A method for producing a perfluoroalkyne compound, comprising producing a perfluoroalkadiene compound using as a substrate a perfluorocycloalkene compound obtained as a by-product in the production method according to claim 6 or 7.

9. The production method according to claim 8, wherein the perfluoroalkyne compound is represented by formula (1): CR 1 2R 2 -C≡C-CR 3 R 4 2(1) where the substituents R 1 -R 4 are the same or different and represent a fluorine atom or a perfluoroalkyl group.

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