RU2780974C1 - Method for producing a perfluoroalkyne compound - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to two variants of a method for producing a perfluoroalkyne compound. According to one variant, the method includes reacting a perfluoroalkadiene compound in the presence of a catalyst in order to produce a perfluoroalkine compound, and satisfies one of the following conditions (C)-(F): (C) the catalyst includes at least one catalyst selected from a group including a fluorinated chromium oxide with a porosity of 0.08 ml/g or more, a fluorinated aluminium oxide with a porosity of 0.35 ml/g or more, and a fluorinated aluminosilicate with a porosity of 0.50 ml/g or more; (D) the catalyst contains a fluorinated metal oxide selected from a group including a fluorinated aluminium oxide and a fluorinated aluminosilicate with a porosity of 0.35 ml/g or more; (E) the catalyst contains a metal oxide fluorinated by interacting the metal oxide with at least one compound selected from a group including hydrofluorocarbon, hydrochlorofluorocarbon, and chlorofluorocarbon, wherein the metal of the metal oxide constitutes at least one element selected from a group including chromium, titanium, silicon, and zirconium; and (F) the catalyst includes one or multiple catalysts produced by fluorinating at least one metal oxide selected from a group including a chromium oxide with a porosity of 0.10 ml/g or more, an aluminium oxide with a porosity of 0.45 ml/g or more, and an aluminosilicate with a porosity of 0.50 ml/g or more. Invention also relates to a catalyst and to a method for producing a catalyst.

EFFECT: possibility of producing a perfluoroalkine compound with high selectivity at a high degree of conversion.

13 cl, 15 tbl, 3 ex, 3 dwg

Description

Technical field

[0001]

The present invention relates to a process for the production of a perfluoroalkyne compound.

State of the art

[0002]

Perfluoroalkyne compounds are compounds that are expected to be useful as a dry etch gas for semiconductors, as well as in various applications, such as coolants, foaming agents and heat transfer fluids. Perfluoroalkyne compounds are compounds that have a triple carbon-carbon bond.

[0003]

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

Citation list

Patent Documents

[0004]

PD 1: JP 2012-001448A

PD 2: JP 2014-058488A

The essence of the invention

Technical task

[0005]

The object of the present invention is to provide a method that can produce a perfluoroalkyne compound with high selectivity at a high conversion rate of the reaction, and which is less likely to produce a fluoroalkene compound as a by-product. Yet another object of the present invention is to provide a process for the production of a perfluoroalkyne compound, wherein the process is capable of reducing degradation (ie deterioration) of the catalyst.

The solution of the problem

[0006]

The present invention includes the following objects.

[0007]

Item 1. A method for producing a perfluoroalkyne compound, comprising reacting a perfluoroalkyne compound in the presence of a catalyst to obtain a perfluoroalkyne compound, and satisfying one of the following conditions (A) to (G):

(A) the catalyst includes 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 3-14 of the periodic table of the elements;

(B) the catalyst includes 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 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;

(D) the catalyst contains a fluorinated metal oxide having a porosity of 0.35 ml/g or more;

(E) the catalyst contains a metal oxide fluorinated by reacting the metal oxide with at least one compound selected from the group consisting of hydrofluorocarbon, hydrochlorofluorocarbon and chlorofluorocarbon;

(F) the catalyst comprises one or more catalysts obtained by fluorination of at least one metal oxide selected from the group consisting of chromium oxide having a porosity of 0.10 ml/g or more, alumina having a porosity of 0.45 ml /g or more, and aluminosilicate having a porosity of 0.50 ml/g or more; and

(G) at least part of the reaction of the perfluoroalkadiene compound from the beginning to the end of the reaction is carried out under conditions under which the water content in the reaction system is 30 wt./million or less, based on the weight of the perfluoroalkadiene compound (taken as 100% wt. ).

[0008]

Item 2 The production method according to item 1, wherein the perfluoroalkyne compound is represented by the formula (1):

CR ¹ ₂ R ² -C≡C-CR ³ R ⁴ ₂ (1)

(wherein 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 the formula (2):

CR ¹ ₂ =CR ² -CR ³ =CR ⁴ ₂ (2)

(wherein the substituents R ¹ -R ⁴ are the same or different and represent a fluorine atom or a perfluoroalkyl group).

[0010]

Item 4. The method of production in accordance with any of items 1-3, where 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 4-6 of the periodic table; and

a catalyst containing at least two elements that belong to groups 4-6 and groups 13 and 14 of the periodic table.

[0011]

Item 5. The method of production in accordance with any of items 1-4, where the method satisfies the condition (A) or (B), and the catalyst is at least one catalyst selected from the group including 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 condition (D) and the fluorinated metal oxide metal 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 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 condition (E) and the metal oxide metal before fluorination includes at least one element which 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 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 yields the 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 the formula (3):

[0020]

,

,

[0021]

(wherein the substituents R ¹ -R ⁴ have the meanings defined above).

[0022]

Item 14. 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 of items 12 or 13.

[0023]

Item 15 The production method according to item 14, wherein the perfluoroalkyne compound is represented by the formula (1):

CR ¹ ₂ R ² -C≡C-CR ³ R ⁴ ₂ (1)

(wherein 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 the formula (1):

CR ¹ ₂ R ² -C≡C-CR ³ R ⁴ ₂ (1)

(wherein the substituents R ¹ -R ⁴ are the same or different and represent a fluorine atom or a perfluoroalkyl group),

perfluorocycloalkene compound is represented by formula (3):

[0025]

,

,

[0026]

(wherein the substituents R ¹ -R ⁴ have the meanings defined above),

wherein the composition contains a perfluoroalkyne compound represented by formula (1) in an amount of 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 etch gas or building block for organic synthesis.

[0028]

Item 18. 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 fluorinated chromium oxide having a porosity of 0.08 ml/g or more, fluorinated alumina having a porosity of 0.35 ml/g or more, and 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 condition (D) and the fluorinated metal oxide metal 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 the reaction of a perfluoroalkadiene compound to produce a perfluoroalkyne compound, comprising the following step (E) or (F):

(E) reacting the metal oxide with at least one compound selected from the group consisting of hydrofluorocarbon, hydrochlorofluorocarbon, and 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, alumina having a porosity of 0.45 ml/g or more, and aluminosilicate having porosity 0.50 ml/g or more.

[0031]

Item 21 The production method according to item 20, wherein the method satisfies 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 condition (E) and the metal oxide metal before fluorination includes at least one element which belongs to groups 3 to 14 of the periodic table.

Positive 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 which is less likely to produce a fluoroalkene compound as a by-product. According to the present invention, a process for producing a perfluoroalkyne compound can also be provided, wherein the process 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 pre-fluorination porosity and degradation rate when 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 the present description, the terms "comprises", "is" and "includes" encompass the concepts of "comprising", "consisting essentially of" and "consisting of". In the present description, the numerical range indicated as "from A to B" means A or more and B or less.

[0036]

1. Catalyst and catalyst production method

The 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 fluorinated chromium oxide having a porosity of 0.08 ml/g or more, fluorinated alumina having a porosity of 0.35 ml/g or more, and 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.

[0037]

[1-1] Catalyst and catalyst production method (No. 1)

In the present invention, the catalyst 1 for use in reacting (isomerizing) a perfluoroalkadiene compound to produce a perfluoroalkyne compound (which may hereinafter be referred to as "isomerization reaction catalyst 1") contains at least one component selected from the group consisting of fluorinated chromium oxide having a porosity of 0.08 ml/g or more, fluorinated alumina having a porosity of 0.35 ml/g or more, and fluorinated aluminosilicate having a porosity of 0.50 ml/g or more. This catalyst satisfies requirement (C) described above. Traditionally used catalysts for the isomerization reaction are not optimized for porosity. It is not clear what catalyst porosity is commonly used. In the present invention, fluorinated metal oxides having certain porosity values are used to increase the reaction conversion rate, reduce catalyst degradation; accordingly, even when the isomerization reaction is carried out for a long period of time, the degradation of the catalyst can be retarded. Therefore, the use of the catalyst of the present invention can reduce the frequency of catalyst replacement and thus is economical.

[0038]

The chromium oxide catalyst is not particularly limited. When chromium oxide is expressed as CrO _m , 1<m<3 is preferred, 1.2<m<2 is more preferred, and 1.3<m<1.8 is even more preferred. When the chromium oxide is expressed as CrO _m ⋅nH ₂ O, the chromium oxide can be hydrogenated to reach a value of n 3 or less, and especially in the range from 1 to 1.5.

[0039]

The following is an example of a method for synthesizing a chromium oxide catalyst.

[0040]

First, an aqueous solution of a chromium salt (chromium nitrate, chromium chloride, chromic alum, chromium sulfate, etc.) is mixed with aqueous ammonia, resulting in a precipitate of chromium hydroxide. The precipitation reaction rate at this time can control the physical properties of chromium hydroxide. A high reaction rate is preferred. The reaction rate depends on the temperature of the reaction solution, the mixing method of the ammonia water (mixing speed), the stirring state, and the like.

[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 1 to 100 hours. The catalyst in this step may be referred to as a catalyst in the chromium hydroxide state. Then the catalyst can be crushed. In terms of granule strength, catalyst activity, etc., the precipitation reaction rate is preferably controlled so that the pulverized powder (for example, a powder having a particle size of 1000 µm or less, in particular, a particle size of 46 to 1000 µm in a fraction of 95%) has particle density from 0.6 to 1.1 g/ml and preferably from 0.6 to 1.0 g/ml. The powder preferably has a BET specific surface area (specific surface area) 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 minutes. The upper limit of the specific surface area is, for example, approximately 220 m ² /g.

[0042]

If necessary, graphite can be mixed into the chromium hydroxide powder in an amount of 3 wt%. or less and granulated with a tableting machine. The size and strength of the granules can be adjusted accordingly.

[0043]

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

[0044]

In terms 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 about 240 m ² /g and more preferably about 220 m ² /g.

[0045]

Examples of the alumina catalyst include α-alumina, activated alumina, and the like. Examples of activated alumina include ρ-alumina, χ-alumina, κ-alumina, ƞ-alumina, pseudo-γ-alumina, γ-alumina, σ-alumina, Ɵ-alumina, and the like. .

[0046]

Aluminosilicate catalysts can also be used as a complex oxide. Aluminosilicate catalysts are complex oxide catalysts containing silica (SiO ₂ ) and alumina (Al ₂ O ₃ ). For example, a catalyst having a silica content of 20 to 90 wt. %, especially 50 to 80 wt. %, can be used. based on the total mass of silicon dioxide and alumina, taken as 100% of the mass.

[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 a high activity, and the fluorination also easily reduces the degradation of the catalyst; accordingly, even when the isomerization reaction is carried out for a long period of time, catalyst degradation can be slowed down by controlling the porosity. Thus, the metal oxide catalyst is used in the form of a fluorinated metal oxide catalyst. A method for fluorinating a metal oxide catalyst is described later.

[0048]

The catalyst of the present invention is prepared 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 0.075 to 1.5 ml/g), the fluorinated alumina has a porosity of 0.35 ml/g or more ( especially 0.40 to 2.0 ml/g) and the fluorinated aluminosilicate has a porosity of 0.50 ml/g or more (especially 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 adhering carbon impairs gas diffusion in the pores, thereby lowering the activity of the catalyst, that is, more likely to cause degradation of the catalyst. On the other hand, an excessively large porosity complicates the production method of the catalyst and increases the production cost.

[0049]

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

[0050]

A method for fluorinating a metal oxide catalyst is, for example, a method including reacting a metal oxide with a fluorinating agent. More specifically, the metal oxide may be fluorinated, for example by flowing a fluorinating agent through the metal oxide. The metal oxide used in such fluorination may be the metal oxide of the fluorinated metal oxide described above.

[0051]

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 conversion rate of the reaction, and also easily reduces catalyst degradation; wherein the degradation of the catalyst can be easily retarded even when the isomerization reaction is carried out for a long period of time. More specifically, the preferred porosity of metal oxide catalysts prior to fluorination, for example, is such that chromium oxide has a porosity of 0.05 ml/g or more (especially 0.075 to 1.5 ml/g), alumina has a porosity of 0.45 ml/g or more (especially 0.50 to 2.5 ml/g) and the aluminosilicate has 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 coated with carbon, which is a by-product of the reaction, and adherent carbon is less likely to interfere with 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) and the like. . 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 may be used singly or in combination of two or more.

[0053]

Conditions for fluorination 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 such fluorination conditions, the content of fluorine atoms is preferably adjusted to fall within the range described above.

[0054]

The perfluoroalkyne compound to be obtained is, for example, the perfluoroalkyne represented by the formula (1):

CR ¹ ₂ R ² -C≡C-CR ³ R ⁴ ₂ (1)

(wherein the substituents R ¹ -R ⁴ are the same or different and represent a fluorine atom or a perfluoroalkyl group).

[0055]

The perfluoroalkyl group represented by R ¹ to 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 conversion rate of the reaction and the yield and selectivity of the resulting perfluoroalkyne compound, the substituents R ¹ to R ⁴ in the formula (1) are all preferably a fluorine atom. The R ¹ -R ⁴ substituents may be the same or different.

[0057]

Thus, the perfluoroalkyne compound of formula (1) to be obtained includes, for example, CF ₃ C≡CCF ₃ , CF ₃ C≡CCF ₂ CF ₃ , CF ₃ C≡CCF(CF ₃ ) ₂ , CF ₃ C≡ CC(CF ₃ ) ₃ , CF ₃ CF ₂ C≡CCF ₂ CF ₃ , CF ₃ CF ₂ C≡CCF(CF ₃ ) ₂ , CF ₃ CF ₂ C≡CC(CF ₃ ) ₃ , (CF ₃ ) ₂ CFC ≡CCF(CF ₃ ) ₂ , (CF ₃ ) ₂ CFC≡CC(CF ₃ ) ₃ , (CF ₃ ) ₃ CC≡CC(CF ₃ ) ₃ etc.

[0058]

The perfluoroalkadiene compound as a substrate is preferably, for example, a perfluoroalkadiene represented by the formula (2):

CR ¹ ₂ =CR ² -CR ³ =CR ⁴ ₂ (2)

(wherein the substituents R ¹ -R ⁴ are the same or different and represent a fluorine atom or a perfluoroalkyl group).

[0059]

The perfluoroalkyl group represented by R ¹ to 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 viewpoint of, for example, the degree of conversion of the reaction and the yield and selectivity of the resulting perfluoroalkyne compound, the substituents R ¹ to R ⁴ in the formula (2) are preferably all fluorine atom. The R ¹ -R ⁴ substituents may be the same or different.

[0061]

Examples of the perfluoroalkadiene of formula (2) which satisfies the conditions described above include CF ₂ ═CFCF=CF ₂ , CF ₂ ═CFCF=CFCF ₃ , CF ₃ CF=CFCF=CFCF ₃ , CF(CF ₃ )=CFCF=CF ₂ , C(CF ₃ ) ₂ =CFCF=CF ₂ , CF(CF ₃ )=CFCF=CF(CF ₃ ), C(CF ₃ ) ₂ =CFCF=CF(CF ₃ ), C(CF ₃ ) ₂ =CFCF= C(CF ₃ ) ₂ , CF ₂ =C(CF ₃ )C(CF ₃ )=CF ₂ etc. These perfluoroalkadienes represented by formula (2) may be used alone or in combination of two or more.

[0062]

The perfluoroalkadiene compound described above may be a known or commercially available product. It is also possible to synthesize the perfluoroalkadiene compound by a conventional method, such as the method described in JP 2001-192345A.

[0063]

[1-2] Catalyst and catalyst production method (No. 2)

In the present invention, the catalyst 2 for use in reacting (isomerizing) a perfluoroalkadiene compound to produce a perfluoroalkyne compound (which may hereinafter be referred to as "isomerization reaction catalyst 2") contains a fluorinated metal oxide having a porosity of 0.35 ml/g or more. This catalyst satisfies requirement (D) described above. Traditionally used catalysts for the isomerization reaction are not optimized for porosity. It is not clear what catalyst porosity is commonly used. In the present invention, fluorinated metal oxides having a certain porosity are used, and the porosity of the fluorinated metal oxides is increased to 0.35 ml/g or more, thereby increasing the reaction conversion rate and also easily reducing catalyst degradation; accordingly, catalyst degradation can be retarded even when the isomerization reaction is carried out for a long period of time. Thus, the use of the catalyst of the present invention can reduce the frequency of catalyst replacement, and hence is economical.

[0064]

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

[0065]

From the viewpoint of having high activity in the isomerization reaction from a perfluoroalkadiene compound to a perfluoroalkyne compound, increasing the reaction conversion rate, as well as easily reducing catalyst degradation and easily inhibiting catalyst degradation even when 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 alumina catalyst, a fluorinated zirconium oxide catalyst or the like.

[0066]

The titanium oxide catalyst that is used may be any catalyst containing titanium dioxide as the main component and may additionally contain one or two or more other non-volatile substances such as metal oxides, hydroxides, sulfates, nitrates, phosphates and metal sulfides. Titanium oxide catalyst preferably contains titanium dioxide in the amount of 70% of the mass. or more.

[0067]

The titanium dioxide is particularly preferably an anthase-form 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, catalysts commercially available 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 [1-1] "Catalyst and Catalyst Production Method (No. 1)" above.

[0069]

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

[0070]

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 down by controlling the porosity. Thus, the metal oxide catalyst is used in the form of a fluorinated metal oxide catalyst. A method for fluorinating a 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 catalyst degradation can be easily retarded 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 0.40 to 2.0 ml/g. The preferred porosity of metal oxide catalysts, for example, is such that the fluorinated alumina has a porosity of 0.35 ml/g or more (especially 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 coated with carbon, which is a by-product of the reaction; and stuck 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 retarded, and the production method of the catalyst is also simple.

[0072]

The degree of fluorination (that is, the content of fluorine atoms) in 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 in [1-1] "Catalyst and catalyst production method (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 conversion rate of the reaction; and also easily reduces catalyst degradation and easily retards 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, and more preferably 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 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 in this range, the active sites of the catalyst are less likely to be coated with carbon, which is a by-product of the reaction; and stuck 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 retarded, and the production method of the catalyst 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 those described in [1-1] "Catalyst and Catalyst Production Method (No. 1)" above.

[0075]

2. Catalyst production method

The method for producing a catalyst of 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 includes the following steps (E) or (F):

(E) reacting the metal oxide with at least one compound selected from the group consisting of hydrofluorocarbon, hydrochlorofluorocarbon, and 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, alumina having a porosity of 0.45 ml/g or more, and aluminosilicate having porosity 0.50 ml/g or more.

[0076]

[2-1] Catalyst production method (No. 3)

In the present invention, a method for producing a catalyst 3 for producing a catalyst for use in the reaction (isomerization) of a perfluoroalkadiene compound to produce a perfluoroalkyne compound (which may hereinafter be referred to as "isomerization reaction catalyst of production method 3") comprises reacting a metal oxide of at least with one compound selected from the group consisting of hydrofluorocarbon and hydrochlorofluorocarbon, for fluorinating the metal oxide. This catalyst satisfies requirement (E) described above. Traditionally used catalysts for the isomerization reaction are not optimized for porosity. It is not clear what catalyst porosity is commonly used. In the present invention, the metal oxide is fluorinated with the specific compound described above to eventually adjust the porosity to fall within a predetermined range, improve the conversion rate of the reaction, and also easily reduce the degradation of the catalyst; accordingly, catalyst degradation can be retarded even when the isomerization reaction is carried out for a long period of time. Thus, the use of the catalyst of the present invention can reduce the frequency of catalyst replacement, and hence is economical.

[0077]

The metal oxide is not particularly limited. From the viewpoint of improving the reaction conversion rate as well as easily reducing catalyst degradation and easily inhibiting catalyst degradation even when isomerization is carried out for a long period of time, the metal oxide metal is preferably, for example, at least one element which belongs to the groups 3-14 of the periodic table; more preferably, at least one element that belongs to groups 4-6 and groups 13 and 14 of the periodic table; and more preferably at least one selected from the group consisting of chromium, titanium, silicon, aluminium, zirconium, and the like. The metal oxide may contain only one, or two, or more of the metal elements described above.

[0078]

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

[0079]

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

[0080]

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 conversion rate of the reaction; and also easily reduces catalyst degradation and easily retards catalyst degradation even when the isomerization reaction is carried out for a long period of time. More specifically, the metal oxide catalyst prior to 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 metal oxide catalysts prior to fluorination is such that, for example, chromium oxide has a porosity of 0.05 ml/g or more (especially 0.075 to 1.5 ml/g), alumina has a porosity of 0.45 ml/g or more (especially 0.50 to 2.5 ml/g) and the aluminosilicate has a porosity of 0.40 ml/g or more (especially 0.50 to 2.0 ml/g). When the porosity is in this range, the active sites of the catalyst are less likely to be coated with carbon, which is a by-product of the reaction; and stuck 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 inhibited, and the production method of the catalyst is also simple.

[0081]

In the present invention, a metal oxide catalyst such as the catalysts described above is fluorinated with a certain compound to obtain a fluorinated metal oxide catalyst. The fluorinated metal oxide catalyst has high activity, and fluorination also easily reduces catalyst degradation; accordingly, the degradation of the catalyst can be slowed down by controlling the porosity even when the isomerization reaction is carried out for a long period of time. Thus, 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 includes reacting a metal oxide with a fluorinating agent. More specifically, the metal oxide may be fluorinated, for example, by passing a 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 the fluorinating agent in this fluorination. Compared with hydrogen fluoride, these fluorinating agents can increase the porosity of the fluorinated metal oxide catalyst and can reduce catalyst degradation and retard catalyst degradation even when the isomerization reaction is carried out for a long period of time. These fluorinating agents may be used singly or in combination of two or more.

[0084]

Conditions for fluorination 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 way has a large porosity. In view of the above, a large porosity reduces catalyst degradation and can slow catalyst degradation even when the isomerization reaction is carried out for a long period of time. More specifically, the metal oxide catalyst after fluorination preferably has a porosity of 0.35 ml/g or more, more preferably 0.40 to 2.0 ml/g. The preferred porosity of metal oxide catalysts, for example, is such that fluorinated chromium oxide has a porosity of 0.05 ml/g or more (especially from 0.075 to 1.5 ml/g), fluorinated alumina has a porosity of 0.35 ml/g or more ( especially 0.40 to 2.0 ml/g) and the 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 coated with carbon, which is a by-product of the reaction; and stuck 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 retarded, and the production method of the catalyst is also simple.

[0086]

The catalyst obtained in this way has a large porosity. The porosity can be adjusted by the degree of fluorination of the catalyst; that is, due to the content of fluorine atoms. Thus, the content of fluorine atoms in the obtained catalyst after fluorination is preferably 5.0 to 50 atom%, more preferably 10 to 25 atom%. 100% atom. 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 [1-1] "Catalyst and Catalyst Production Method (No. 1)" above.

[0088]

[2-2] Catalyst production method (No. 4)

In the present invention, a method for producing a catalyst 4 for producing a catalyst for use in the reaction (isomerization) of a perfluoroalkadiene compound to produce a perfluoroalkyne compound (which may hereinafter be referred to as "isomerization reaction catalyst of production method 4") comprises fluorination of at least one oxide a metal selected from the group consisting of chromium oxide having a porosity of 0.10 ml/g or more before metal oxide fluorination, alumina having a porosity of 0.45 ml/g or more before metal oxide fluorination, and aluminosilicate having a porosity of 0, 5 ml/g or more before metal oxide fluorination. This catalyst satisfies requirement (F) described above. Traditionally used catalysts for the isomerization reaction are not optimized for porosity. It is not clear what catalyst porosity is commonly used. In the present invention, metal oxides having a certain porosity are fluorinated to increase the conversion rate of the reaction and also to easily reduce the degradation of the catalyst; accordingly, catalyst degradation can be retarded even when the isomerization reaction is carried out for a long period of time. Thus, the use of the catalyst of the present invention can reduce the frequency of catalyst replacement, and hence is economical.

[0089]

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

[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 conversion rate of the reaction; and can also 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. More specifically, the preferred porosity of metal oxide catalysts prior to fluorination is such that chromium oxide has a porosity of 0.05 ml/g or more (especially 0.075 to 1.5 ml/g), alumina has a porosity of 0.45 ml/g or more ( especially 0.50 to 2.5 ml/g), and the aluminosilicate has a porosity of 0.40 ml/g or more (especially 0.50 to 2.0 ml/g). When the porosity is smaller than this range, the pores where the active sites of the catalyst are located are covered with carbon, which is a by-product of the reaction, or the adhered carbon prevents gas from diffusing into the pores, thereby reducing the activity of the catalyst, that is, more likely to cause degradation of the catalyst. . On the other hand, an excessively large porosity complicates the production method of the catalyst and increases the production cost.

[0091]

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, the degradation of the catalyst can be slowed down by controlling the porosity even when the isomerization reaction is carried out for a long period of time. Thus, the metal oxide catalyst is used in the form of a fluorinated metal oxide catalyst.

[0092]

The fluorination method, fluorinating agent, fluorination conditions, and the like. may be the same as described above in [1-1] "Catalyst and Catalyst Production Method (No. 1)".

[0093]

The catalyst obtained in this way has a large porosity. Considering the above, large porosity reduces catalyst degradation and catalyst degradation can be 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, 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 the 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 coated with carbon, which is a by-product of the reaction; and stuck 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 retarded, and the production method of the catalyst is also simple.

[0094]

The catalyst obtained in this way has a large porosity. The porosity can be adjusted by the degree of fluorination of the catalyst; that is, due to the content of fluorine atoms. Thus, the content of fluorine atoms in the obtained catalyst after fluorination is preferably 5.0 to 50 atom%, more preferably 10 to 25 atom%, per 100% atom. the total amount of catalyst after fluorination.

[0095]

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

[0096]

3. Method for the production of a perfluoroalkyne compound

The method for producing a perfluoroalkyne compound according to the present invention includes 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 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 3-14 of the periodic table of the elements;

(B) the catalyst contains 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 contains 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 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;

(D) the catalyst contains a fluorinated metal oxide having a porosity of 0.35 ml/g or more;

(E) the catalyst contains a metal oxide fluorinated by reacting at least one compound selected from the group consisting of hydrofluorocarbon, hydrochlorofluorocarbon and chlorofluorocarbon with the metal oxide;

(F) the catalyst contains one or more catalysts obtained by fluorination of at least one metal oxide selected from the group consisting of chromium oxide having a porosity of 0.10 ml/g or more, alumina having a porosity of 0.45 ml/g g or more, and aluminosilicate having a porosity of 0.50 ml/g or more; and

(G) at least part of the reaction of the perfluoroalkadiene compound from the beginning to the end of the reaction is carried out under conditions under which the reaction system has a water content of 30 mass/million or less, based on the mass of the perfluoroalkadiene compound taken as 100 wt%.

[0097]

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

[0098]

[3-1] Production method of perfluoroalkyne compound (No. 1)

The first method for producing a perfluoroalkyne compound according to the present invention comprises reacting a perfluoroalkyne compound in the presence of a catalyst to produce 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 3-14 of the periodic table. This production method satisfies requirement (A) described above.

[0099]

The well-known methods for producing a perfluoroalkyne compound are limited to methods using a catalyst containing only one element that belongs to group 13 of the periodic table and does not contain any transition metals; or a catalyst containing an alkali metal. In accordance with the present invention, a catalyst containing a transition metal element, or a catalyst containing at least two elements that belong to groups 3-14 of the periodic table, neither of which is traditionally used, is used to achieve a high degree of conversion as a result. reaction and obtain a perfluoroalkyne compound in high yield and high selectivity, thereby expanding the freedom of choice in the synthesis of the perfluoroalkyne compound. Thus, by using as a catalyst, for example, a catalyst containing a transition metal element having a high activity, or a catalyst containing at least two elements that belong to groups 3 to 14 of the periodic table, which has a higher activity in mixed oxide form, the perfluoroalkyne compound can be produced with high selectivity at high reaction conversion. Moreover, in accordance with the present invention, in contrast to conventional methods, it is less likely that a fluoroalkene compound will be formed as a by-product, as described below.

[0100]

In the present invention, a catalyst containing a transition metal element or a catalyst containing at least two elements that belong 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 obtaining a perfluoroalkyne compound in high yield and high selectivity, the catalyst to be used, for example, is preferably a catalyst containing at least one transition metal element which belongs to groups 4- 6 of the periodic table, or a catalyst containing at least two elements that belong to groups 4-6 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), optionally fluorinated titanium oxide catalyst (titanium oxide catalyst or fluorinated titanium oxide catalyst), optionally fluorinated zirconium oxide catalyst (zirconium oxide catalyst or fluorinated zirconium oxide catalyst) or optionally a fluorinated aluminosilicate catalyst (aluminosilicate catalyst or fluorinated aluminosilicate catalyst), since such catalysts are highly active in the isomerization reaction from a perfluoroalkadiene compound to a perfluoroalkyne compound; and may also have high activity in the reaction of formation of a perfluorocycloalkene compound depending on the reaction conditions, wherein the perfluorocycloalkene compound as well as the perfluoroalkyne compound are expected to be useful as a dry etch gas for semiconductors, as well as in various applications, for example, as coolants, foaming agents and heat transfer fluids.

[0102]

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

[0103]

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

[0104]

These isomerization reaction catalysts may be used singly 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 conversion rate of the reaction 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 0.1 to 200 g⋅sec /cc and more preferably from 0.5 to 150 g⋅sec/cc. When using two or more catalysts for the isomerization reaction, it is preferable to control the total amount of catalysts within the above range. The above W/F ratio specifies the amount of 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 may be adjusted accordingly.

[0106]

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

[0107]

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

[0108]

In the production method of the present invention, the reaction of the perfluoroalkadiene compound is preferably carried out with heating. More specifically, heating is preferably carried out after the perfluoroalkadiene compound as a substrate and the isomerization reaction catalyst are placed in the reaction system. The heating temperature of such heating is preferably 170°C or more (for example, 170 to 400°C) and more preferably 180 to 280°C in view of achieving a particularly high reaction conversion and obtaining a 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 view of achieving a particularly high reaction conversion and obtaining a perfluoroalkyne compound in high yield and high selectivity.

[0110]

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

[0111]

In the production method of the present invention, not only a perfluoroalkyne compound but also a perfluorocycloalkene compound can be produced. Examples of the perfluorocycloalkene compound include the perfluorocycloalkene compounds represented by the formula (3):

[0112]

,

,

[0113]

(wherein the substituents R ¹ -R ⁴ have the meanings defined above). Details of the perfluorocycloalkene compound are described below.

[0114]

Thus, after the completion of the reaction, purification is carried out in accordance with 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 in a conventional manner if necessary; and then used as a substrate to obtain a perfluoroalkyne compound. The method and conditions in this process may be the same as those described in Patent Document (PD) 2 (JP 2014-058488A). Preferred specific examples may be those described in AP 2.

[0116]

More specifically, when using a perfluorocycloalkene compound as a substrate, isomerization is carried out with an isomerization reaction catalyst, resulting in a perfluoroalkyne compound. This step can be carried out in the gas phase, especially in a gas phase continuous flow process using a fixed bed reactor. On the other hand, this step can also be carried out by 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, high activity and high selectivity. When sodium fluoride itself is used as the catalyst, it may be in the form of a powder. Sodium fluoride in the form of granules is preferred for gas-phase continuous flow reaction. You can also use sodium fluoride supported on a carrier such as alumina, porous aluminum fluoride, activated carbon, silica or zeolite. On the other hand, sodium fluoride can be mixed with other components and then used.

[0118]

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

[0119]

The perfluorocycloalkene compound as well as the perfluoroalkyne compound obtained as described above can be successfully used as an etch gas to form advanced microstructures such as semiconductors and liquid crystals; and also in various fields of application, for example, as building blocks for organic synthesis. Details of building blocks for organic synthesis are described later.

[0120]

[3-2] Production method of perfluoroalkyne compound (No. 2)

The second method for producing a perfluoroalkyne compound according to the present invention is a process comprising reacting a perfluoroalkyne compound in the presence of a catalyst to obtain a perfluoroalkyne compound, wherein the catalyst contains 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 requirement (B) described above.

[0121]

Conventional methods for producing a perfluoroalkyne compound include methods using a catalyst containing only one element which belongs to group 13 of the periodic table and does not contain 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 which belongs to group 13 of the periodic table and does not contain any transition metals, there are only cases in which the reaction time is long; that is, 32 sec or longer. According to the present invention, by using a catalyst containing at least one element belonging to groups 3 to 14 of the periodic table and reducing the reaction time to 30 seconds or less, a high reaction conversion is achieved and a 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, a fluoroalkene compound is less likely to be produced as a by-product, as described later.

[0122]

In the present invention, a catalyst containing at least one element that belongs 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 point of view of achieving a particularly high reaction conversion and obtaining a perfluoroalkyne compound with a higher yield and higher selectivity, catalysts containing a transition metal element and catalysts containing at least two elements that belong to groups 3 to 14 of the periodic table are preferred. . Catalysts containing at least one transition metal element that belongs to groups 4-6 of the periodic table, and catalysts containing at least two elements that belong to groups 4-6 and groups 13 and 14 of the periodic table, are more preferred. Chromium, titanium and zirconium containing catalysts, silicon and aluminum containing catalysts 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), optionally fluorinated titanium oxide catalyst (titanium oxide catalyst or fluorinated titanium oxide catalyst), optionally fluorinated zirconium oxide catalyst (zirconium oxide catalyst or fluorinated zirconium oxide catalyst) or optionally a fluorinated aluminosilicate catalyst (aluminosilicate catalyst or a fluorinated aluminosilicate catalyst), since such catalysts have a high activity in the isomerization reaction from a perfluoroalkadiene compound to a perfluoroalkyne compound, and may also have a high activity in the formation reaction of 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 gas. o etching for semiconductors, as well as in various applications, for example, as coolants, foaming agents, heat transfer fluids, etc. In this embodiment, an 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 [1-1] "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 [1-2] "Catalyst and Catalyst Production Method (No. 2)" above.

[0125]

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

[0126]

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

[0127]

The amount of the isomerization reaction catalyst described above may be the same as the amount described in [3-1] "Production Method of Perfluoroalkyne Compound (No. 1)" above.

[0128]

In the production method of the present invention, when the reaction of the perfluoroalkadiene compound is carried out, nickel metal (particularly nickel metal 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/cc, in particular 0.5 to 150 g⋅sec/cc, for purposes of heat transfer and dilution of catalyst concentration.

[0129]

The production process of the present invention (particularly the reaction of the perfluoroalkadiene compound) can be carried out in the liquid phase, but 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 equipment, operation, etc. compared to carrying out the reaction in a liquid phase, and can also provide 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 reacting the perfluoroalkadiene compound may be the same as described above in [3-1] Production method of 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]

In the production method of the present invention, not only a perfluoroalkyne compound but also a perfluorocycloalkene compound can be produced. Examples of the perfluorocycloalkene compound include the perfluorocycloalkene compounds represented by the formula (3):

[0133]

,

,

[0134]

(wherein 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 the usual way, 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 to obtain the perfluoroalkyne compound. The production method and conditions of the perfluoroalkyne compound in this process may be the same as those described above in [3-1] "Production method of the perfluoroalkyne compound (No. 1)".

[0137]

The perfluorocycloalkene compound as well as the perfluoroalkyne compound obtained in this way can be successfully used as an etch gas to form advanced microstructures such as semiconductors and liquid crystals; and also in various applications, for example as building blocks for organic synthesis. Detailed information on the building block for organic synthesis is presented later.

[0138]

[3-3] Production method of perfluoroalkyne compound (No. 3)

The third method for producing a perfluoroalkyne compound according to the present invention is a process comprising reacting a perfluoroalkyne compound in the presence of a catalyst to obtain a perfluoroalkyne compound and satisfying one of the following conditions (C) to (F):

(C) the catalyst contains 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 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;

(D) the catalyst contains a fluorinated metal oxide having a porosity of 0.35 ml/g or more;

(E) the catalyst contains a metal oxide fluorinated by reacting the metal oxide with at least one compound selected from the group consisting of hydrofluorocarbon, hydrochlorofluorocarbon, and chlorofluorocarbon; and

(F) the catalyst contains one or more catalysts obtained by fluorination of at least one metal oxide selected from the group consisting of chromium oxide having a porosity of 0.10 ml/g or more, alumina having a porosity of 0.45 ml/g g or more, and aluminosilicate having a porosity of 0.50 ml/g or more.

[0139]

The requirement (C) means that the isomerization reaction catalyst 1 of the present invention described in [1-1] "Catalyst and Catalyst Production Method (No. 1)" above is used. The requirement (D) means that the isomerization reaction catalyst 2 of the present invention described in [1-2] "Catalyst and Catalyst Production Method (No. 2)" above is used. The requirement (E) means that the catalyst obtained by the isomerization reaction catalyst production method 3 described in [2-1] "Catalyst production method (No. 3)" above is used. The requirement (F) means that the catalyst obtained by the isomerization reaction catalyst production method 4 described in [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]

In the present invention, the above-described catalyst of the invention is used, whereby the conversion rate of the reaction is increased and the degradation of the catalyst is also easily reduced; accordingly, even when the isomerization reaction is carried out for a long period of time, the degradation of the catalyst can be retarded. Thus, the use of the catalyst of 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 may be a catalytic amount and is not particularly limited. From the viewpoint of achieving a particularly high reaction conversion rate, as well as 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 catalyst to perfluoroalkadiene compound feeding rate per hour (W/F) is preferably 0.1 to 200 g⋅sec/cc, and more preferably 0.5 to 150 g⋅sec/cc. When using two or more catalysts for the isomerization reaction, it is preferable to adjust the total amount of catalysts so that it is in the above range. The above W/F ratio accurately determines the amount of 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, nickel metal (particularly, metallic nickel balls), activated carbon or the like, in addition to the perfluoroalkadiene compound as a substrate and catalyst for the isomerization reaction, can also be used in such an amount as to obtain a W/F ratio from 0.1 to 200 g⋅sec/cc, in particular from 0.5 to 150 g⋅sec/cc, for purposes of heat transfer and dilution of catalyst concentration.

[0143]

In the production method of the present invention, the isomerization reaction can be carried out in the liquid phase, but preferably it is carried out in the gas phase, especially in a gas phase continuous flow process using a fixed bed reactor. This can make equipment, work, etc. easier. compared to carrying out the reaction in a liquid phase, and can also give a perfluoroalkyne compound in higher yield and higher selectivity than carrying out the reaction in a batch system. Moreover, it easily reduces the degradation of the catalyst, and even when the isomerization reaction is carried out for a long period of time, the degradation of the catalyst can be easily retarded.

[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 of such heating is preferably 170°C or more (especially 170 to 400°C) and more preferably 180 to 280°C from the viewpoint of achieving a particularly high reaction conversion, easily reducing catalyst degradation, and easily inhibiting 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 retards 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, if necessary, purification can be carried out in a conventional manner, and as a result, a perfluoroalkyne compound can be obtained.

[0148]

The perfluoroalkyne compound obtained as described above can be successfully used as an etch gas to form advanced microstructures such as semiconductors and liquid crystals; and also in various fields of application, for example, as building blocks for organic synthesis. Detailed information on the structural block for organic synthesis will be presented below.

[0149]

[3-4] Production method of perfluoroalkyne compound (No. 4)

The fourth method for producing a perfluoroalkyne compound according to the present invention is a method comprising reacting a perfluoroalkyne compound in the presence of a catalyst to obtain a perfluoroalkyne compound, wherein at least a portion of the reaction of the perfluoroalkyne compound from the beginning to the end of the reaction is carried out under conditions under which the water content in the reaction system is 30 mass/million or less, based on the weight of the perfluoroalkadiene compound (taken as 100% by mass).

[0150]

As a method for producing a perfluoroalkyne compound, a method is known which includes reacting and isomerizing a perfluoroalkadiene compound in the presence of a catalyst. However, no method is known that is capable of reducing catalyst degradation. According to the present invention, the reaction system has a water content of 30 ppmw or less, based on the weight of the perfluoroalkadiene compound (100% wt.), at least in part of the reaction from the beginning to the end of the reaction, to thereby reduce the degradation catalyst and maintain a high degree of conversion of the reaction; accordingly, catalyst degradation can also be retarded even when the isomerization reaction is carried out for a long period of time. In addition, since the catalyst degradation rate also varies depending on the mass ratio of catalyst to perfluoroalkadiene compound feed rate per hour (W/F), catalyst degradation can be further retarded by increasing the W/F ratio; that is, by slowing down the feed rate of the perfluoroalkadiene compound. Thus, by using the production method according to the present invention, the replacement frequency of the catalyst 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 of the reaction system is controlled to a low level. This can effectively prevent water from covering the active sites of the catalyst and causing degradation of the catalyst. That is, no matter what type of catalyst is used, the method according to the present invention can prevent water from coating 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 of the reaction system, so as to easily reduce catalyst degradation and easily slow down catalyst degradation 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 an element that belongs to groups 3-14 of the periodic table; more preferably a catalyst containing at least one element that belongs to groups 4-6 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 from a perfluoroalkadiene compound to a perfluoroalkyne compound, easily reducing catalyst degradation by lowering the water content of the reaction system, and easily slowing down catalyst degradation even when the isomerization reaction is carried out for a long period of time, the isomerization reaction catalyst is particularly preferable. is an optionally fluorinated chromium oxide catalyst (chromium oxide catalyst or fluorinated chromium oxide catalyst), optionally fluorinated titanium oxide catalyst (titanium oxide catalyst or fluorinated titanium oxide catalyst), optionally fluorinated alumina catalyst (alumina catalyst or fluorinated alumina catalyst), or 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 [1-1] "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 [1-2] "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), the fluorination method, the fluorinating agent, and the fluorination conditions may be the same as those described in [1-1] "Catalyst and Catalyst Production Method (No. 1)" above.

[0156]

The amount of the isomerization reaction catalyst described above may be the same amount as described above in section [3-1] "Production method of perfluoroalkyne compound (No. 1)".

[0157]

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

[0158]

In the production method of the present invention, at least part of the isomerization reaction from the beginning to the end of the reaction (the reaction of the perfluoroalkadiene compound) is carried out under conditions under which the reaction system has a water content of 30 mass/million or less, preferably 20 mass. ./million or less, based on the weight of the perfluoroalkadiene compound (taken as 100% wt.). The lower limit of the water content can be 1 wt.h./million. In the present invention, the water content of the reaction system can be controlled, for example, by supplying a perfluoroalkadiene compound having a certain water content, while the reaction atmosphere is an inert gas atmosphere, as described below.

[0159]

In the present invention, the water content of the reaction system is 30 ppm or less, as described above. The reaction system may have a water content of 30 mass/million 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 mass/million or less, at least in part of the reaction start to end of the reaction (at least at any time). From the point of view of more effectively slowing down the degradation of the catalyst, the reaction system preferably has a water content of 30 mass/million or less (in particular, 20 mass/million or less), at least at the beginning of the reaction. It is particularly preferred that the water content of the reaction system is maintained at 30 ppmw or less (particularly 20 ppmw or less) throughout the reaction from the start 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 of 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 or less in the reaction system can be expressed as the perfluoroalkadiene compound used as a substrate substantially has a water content of 30 ppm 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 reacting a perfluoroalkadiene compound having a water content of 30 ppm or less in the presence of a catalyst to produce a perfluoroalkyne connections. Again, the perfluoroalkyne compound may have a water content of 30 ppm by mass or less at the start of the reaction, more particularly immediately before being contacted with the catalyst; the perfluoroalkyne compound in the reaction system may have a water content of 30 ppm or less at some point during the reaction; or the perfluoroalkyne compound may have a water content of 30 ppm or less immediately after the end of the reaction. That is, it is sufficient if the perfluoroalkyne compound has a water content of 30 ppmw or less for at least part of the reaction from the beginning 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 or less throughout the entire reaction from the beginning to the end of the reaction.

[0161]

In the production method of the present invention, the isomerization reaction (reaction of the perfluoroalkadiene compound) 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 to carrying out the reaction in a liquid phase; and can also give the perfluoroalkyne compound in higher yield and higher selectivity than carrying out the reaction in a batch system. Moreover, reducing the water content of the reaction system makes it easier to reduce catalyst degradation, and catalyst degradation can be easily retarded 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 in [3-1] "Production method of the perfluoroalkyne compound (No. 1)" above.

[0163]

In the production method of the present invention, the reaction time in carrying out the isomerization reaction (reaction of the perfluoroalkadiene compound) is not particularly limited. Since the production method of the present invention easily reduces the degradation of the catalyst and slows down the degradation of the catalyst 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 in accordance with 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 etch gas to form advanced microstructures such as semiconductors and liquid crystals; as well as in various fields of application, for example, as building blocks for organic synthesis. Detailed information on the building block for organic synthesis is provided below.

[0166]

4. Perfluoroalkyne composition

Perfluoroalkyne compounds can be prepared as described above. However, using the production method described in section "3-1] "Production method of perfluoroalkyne compound (No. 1)" or section [3-2] "Production method of perfluoroalkyne compound (No. 2)" above also seems to give the product in the form of a perfluoroalkyne composition containing a perfluoroalkyne compound and a perfluoro-cycloalkene compound as described above. Using the production method described in section [3-3] "Process for the production of perfluoroalkyne compound (No. 3)" or section [3-4] "Process for the production of perfluoroalkyne compound (No. 4)" above can lead to extremely high selectivity with respect to the obtained perfluoroalkyne compound. compounds and can greatly reduce the content of other additional compounds in the product.

[0167]

When the perfluoroalkyne compound is produced in the form of a perfluoroalkyne composition, the perfluoroalkyne compound is preferably a perfluoroalkyne represented by the formula (1):

CR ¹ ₂ R ² -C≡C-CR ³ R ⁴ ₂ (1),

where the substituents R ¹ -R ⁴ have the meanings defined above, and

the perfluorocycloalkene compound is preferably the perfluorocycloalkene compound represented by the formula (3):

[0168]

,

,

[0169]

where 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 alone or in combination of two or more.

[0170]

Examples of perfluorocycloalkene compounds include the following compounds.

[0171]

[0172]

The perfluorocycloalkene compounds may be used singly or in combination of two or more.

[0173]

In the perfluoroalkyne composition of the present invention, the content of the perfluoroalkyne compound is preferably 40 to 99.999 mole %, more preferably 50 to 99.998 mole %. and even more preferably 60 to 99.997 mol%. based on the total amount of the perfluoroalkyne composition of the present invention, taken as 100 mol%. Similarly, the content of the perfluorocycloalkene compound is preferably 0.001 to 60 mole %, more preferably 0.002 to 50 mole %. and even more preferably from 0.003 to 40 mol%. based on the total amount of the perfluoroalkyne composition of the present invention, taken as 100 mol%.

[0174]

In addition to the perfluoroalkyne compounds and perfluorocycloalkene compounds above, the production method of the present invention can also produce, for example, the perfluoroalkene compound represented by formula (4A):

CR ¹ ₂ =CR ² -CFR ³ -CFR ⁴ ₂ (4A),

where the substituents R ¹ -R ⁴ have the meanings defined above, and

the fluoroalkene compound represented by the formula (4B):

CFR ¹ ₂ -CR ² =CH-CFR ⁴ ₂ (4B),

where the substituents R ¹ -R ⁴ have the meanings defined above.

However, according to the production method of the present invention, the fluoroalkene compound represented by the formula (4B) is hardly produced 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 present in the perfluoroalkyne composition of the present invention, its content is preferably 0.0005 to 0.5 mol %. and more preferably from 0.001 to 0.3 mol%. based on the total amount of the perfluoroalkyne composition of the present invention, taken as 100 mol%. In addition, when the fluoroalkene compound represented by formula (4B) is present in the perfluoroalkyne composition of the present invention, its content is preferably 0 to 0.3 mol %. and more preferably from 0.01 to 0.28 mol%. based on the total amount of the perfluoroalkyne composition of the present invention taken as 100 mole %, since the fluoroalkene compound represented by the formula (4B) is unlikely to be produced as a by-product in the production method of the present invention.

[0176]

According to the production method of the present invention, the perfluoroalkyne compound can be obtained, in particular, in high yield and high selectivity as described above, even when it is obtained as a perfluoroalkyne composition. Thus, 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 applications, for example, as an etch gas used to form advanced microstructures (for example, 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 CF ₃ Si(CH ₃ ) ₃ and introducing a fluoroalkyl group such as _CF3 .

[0178]

Embodiments in accordance with the present invention are described below; however, various changes in form and detail may be made without departing from the spirit and scope of the claims.

Examples

[0179]

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: Cr ₂ O ₃

Fluorinated Chromium Oxide Catalyst (1): Cr ₂ O ₃ is fluorinated by allowing hydrogen fluoride to pass through at atmospheric pressure at 100 to 460° C. for 3 to 4 hours.

Titanium oxide catalyst: TiO ₂

Fluorinated Titanium Oxide Catalyst: TiO ₂ is fluorinated by allowing hydrogen fluoride to pass through at atmospheric pressure at room temperature to 300° C. for 3 to 4 hours.

Fluorinated Zirconium Oxide Catalyst: ZrO ₂ is fluorinated by allowing hydrogen fluoride to pass through at atmospheric pressure at room temperature to 400° C. for 3 to 4 hours.

Aluminosilicate catalyst: SiO ₂ /Al ₂ O ₃ 80/10 to 60/20 (weight ratio).

[0181]

Example 1-1 Fluorinated Chromium Oxide Catalyst; W/F=30.0 g⋅sec/cc; 200 ° C; 23.1 sec

As a catalyst, the fluorinated chromium oxide catalyst (1) (chromium oxide fluorinated with hydrogen fluoride) is loaded into a metal tubular reactor. The reaction tube is heated to 200°C and hexafluorobutadiene (CF ₂ CF=CFCF ₂ ) is fed into the reaction tube until a W/F ratio of 30.0 g⋅sec/cc is reached to allow the reaction to proceed in a 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 was 100 mol % and the selectivity for each component was as follows: 99.7 mol %. for 1,1,1,4,4,4-hexafluoro-2-butyne (CF ₃ C≡CCF ₃ ), 0.162 mol %. for 1,2,3,3,4,4-hexafluoro-1-cyclobutene (c-C ₄ F ₆ ), 0.0356 mol %. for 1,1,2,3,3,4,4,4-octafluoro-1-butene (CF ₂ =CFCF ₂ CF ₃ ) (total E-isomer and Z-isomer), 0.0947 mol %. for 1,1,1,2,4,4,4-heptafluoro-2-butene (CF ₃ CF=CHCF ₃ ) (total E-isomer and Z-isomer) and 0.0182 mol %. for all other by-products.

[0182]

Example 1-2 Fluorinated Chromium Oxide Catalyst; W/F=30.0 g⋅sec/cc; 250 ° C; 23.1 sec

The 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 seconds. 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 for each component was as follows: 97.2 mol %. for 1,1,1,4,4,4-hexafluoro-2-butyne (CF ₃ C≡CCF ₃ ), 2.47 mol %. for 1,2,3,3,4,4-hexafluoro-1-cyclobutene (c-C ₄ F ₆ ), 0.0871 mol%. for 1,1,2,3,3,4,4,4-octafluoro-1-butene (CF ₂ =CFCF ₂ CF ₃ ) (total E-isomer and Z-isomer), 0.262 mol %. for 1,1,1,2,4,4,4-heptafluoro-2-butene (CF ₃ CF=CHCF ₃ ) (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/cc; 200 ° C; 69.3 sec

The 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 90.0 g⋅sec/cc for 69.3 seconds. 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: 99.7 mol %. for 1,1,1,4,4,4-hexafluoro-2-butyne (CF ₃ C≡CCF ₃ ), 0.118 mol %. for 1,2,3,3,4,4-hexafluoro-1-cyclobutene (c-C ₄ F ₆ ), 0.0254 mol %. for 1,1,2,3,3,4,4,4-octafluoro-1-butene (CF ₂ =CFCF ₂ CF ₃ ) (total E-isomer and Z-isomer), 0.0911 mol %. for 1,1,1,2,4,4,4-heptafluoro-2-butene (CF ₃ CF=CHCF ₃ ) (total 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/cc; 200 ° C; 32.5 sec

The reaction was carried out in the same manner as in Example 1-1, except that the reaction was carried out for 32.5 seconds 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 99.0 mole % and the selectivity for each component was as follows: 99.3 mole %. for 1,1,1,4,4,4-hexafluoro-2-butyne (CF ₃ C≡CCF ₃ ), 0.354 mol %. for 1,2,3,3,4,4-hexafluoro-1-cyclobutene (c-C ₄ F ₆ ), 0.0595 mol%. for 1,1,2,3,3,4,4,4-octafluoro-1-butene (CF ₂ =CFCF ₂ CF ₃ ) (total E-isomer and Z-isomer), 0.0341 mol %. for 1,1,1,2,4,4,4-heptafluoro-2-butene (CF ₃ CF=CHCF ₃ ) (total 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/cc; 250 ° C; 32.5 sec

The 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 seconds 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 (CF ₃ C≡CCF ₃ ), 76.0 mol %. for 1,2,3,3,4,4-hexafluoro-1-cyclobutene (c-C ₄ F ₆ ), 0.00110 mol%. for 1,1,2,3,3,4,4,4-octafluoro-1-butene (CF ₂ =CFCF ₂ CF ₃ ) (total E-isomer and Z-isomer), 0.00421 mol %. for 1,1,1,2,4,4,4-heptafluoro-2-butene (CF ₃ CF=CHCF ₃ ) (total 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/cc; 300 ° C; 32.5 sec

The 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 seconds 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 is analyzed by gas chromatography, which shows that the conversion is 100 mol%, and the selectivity for each component is as follows: 44.5 mol%. for 1,1,1,4,4,4-hexafluoro-2-butyne (CF₃C≡CCF₃), 55.1% mol. for 1,2,3,3,4,4-hexafluoro-1-cyclobutene (c-C_fourF₆), 0.00601% mol. for 1,1,2,3,3,4,4,4-octafluoro-1-butene (CF₂=CFCF₂CF₃) (total amount of E-isomer and Z-isomer), 0.00200% mol. for 1,1,1,2,4,4,4-heptafluoro-2-butene (CF₃CF=CHCF₃) (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=30.0 g⋅sec/cc; 250 ° C; 14.9 sec

The 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 seconds using a fluorinated zirconium oxide catalyst (zirconium 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 70.1 mol % and the selectivity for each component was as follows: 4.18 mol %. for 1,2,3,3,4,4-hexafluoro-1-cyclobutene (c-C_fourF₆), 94.1 mol%. for 1,1,1,4,4,4-hexafluoro-2-butyne (CF₃C≡CCF₃), 0.00100% mol. for 1,1,2,3,3,4,4,4-octafluoro-1-butene (CF₂=CFCF₂CF₃) (total amount of E-isomer and Z-isomer), 0.198 mol%. for 1,1,1,2,4,4,4-heptafluoro-2-butene (CF₃CF=CHCF₃) (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/cc; 350 ° C; 14.9 sec

The 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 seconds using a fluorinated zirconium oxide catalyst (zirconium dioxide fluorinated with hydrogen fluoride) as a catalyst. One hour after the completion of the reaction, the gas exiting the reaction tube is analyzed by gas chromatography, which shows that the conversion is 99.5 mol%, and the selectivity for each component is as follows: 2.68 mol%. for 1,1,1,4,4,4-hexafluoro-2-butyne (CF₃C≡CCF₃), 96.3 mol%. for 1,2,3,3,4,4-hexafluoro-1-cyclobutene (c-C_fourF₆), 0.0127 mol%. for 1,1,2,3,3,4,4,4-octafluoro-1-butene (CF₂=CFCF₂CF₃) (total amount of E-isomer and Z-isomer), 0.118 mol%. for 1,1,1,2,4,4,4-heptafluoro-2-butene (CF₃CF=CHCF₃) (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=15.0 g⋅sec/cc; 350 ° C; 7.5 sec

The reaction is carried out in the same manner as in Example 1-1, except that the reaction is carried out at a heating temperature of 350°C with a W/F ratio of 15.0 g⋅sec/cc for 7.5 seconds using as a catalyst for a fluorinated zirconium oxide catalyst (zirconium dioxide fluorinated with hydrogen fluoride). 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 for each component was as follows: 3.71 mol %. for 1,1,1,4,4,4-hexafluoro-2-butyne (CF ₃ C≡CCF ₃ ), 95.3 mol %. for 1,2,3,3,4,4-hexafluoro-1-cyclobutene (c-C ₄ F ₆ ), 0.0163 mol %. for 1,1,2,3,3,4,4,4-octafluoro-1-butene (CF ₂ =CFCF ₂ CF ₃ ) (total E-isomer and Z-isomer), 0.0851 mol %. for 1,1,1,2,4,4,4-heptafluoro-2-butene (CF ₃ CF=CHCF ₃ ) (total E-isomer and Z-isomer) and 0.246 mol %. for all other by-products.

[0190]

Table 1 shows the results of examples 1-1 to 1-9.

[0191]

Table 1

Example 1-1 1-2 1-3 1-4 1-5 1-6 1-7 1-8 1-9 Catalyst Fluorinated chromium oxide Fluorinated chromium oxide Fluorinated chromium oxide Fluorinated titanium dioxide Fluorinated titanium dioxide Fluorinated titanium dioxide Fluorinated zirconia Fluorinated zirconia Fluorinated zirconia W/F 30.0 30.0 90.0 30.0 30.0 30.0 30.0 30.0 15.0 Temperature (°C) 200 250 200 200 250 300 250 350 350 Contact time (sec) 23.1 23.1 69.3 32.5 32.5 32.5 14.9 14.9 7.5 Conversion (mol %) 100 100 100 99.0 99.9 100 70.1 99.5 99.1 Selectivity (mol %) _{CF3 C≡CCF3} 99.7 97.2 99.7 99.3 23.7 44.5 94.1 2.68 3.71 c-C ₄ F ₆ 0.162 2.47 0.118 0.354 76.0 55.1 4.18 96.3 95.3 _{CF2 = CFCF2CF3} 0.0356 0.0871 0.0254 0.0595 0.00110 0.00601 0.00100 0.0127 0.0163 _CF3 CF= _CHCF3 0.0947 0.262 0.0911 0.0341 0.00421 0.00200 0.198 0.118 0.0851 Other 0.0182 0.0194 0.0162 0.213 0.295 0.392 0.0760 0.274 0.246 Total 100 100 100 100 100 100 100 100 100

[0192]

Example 1-10 Fluorinated Chromium Oxide Catalyst; W/F=15.0 g ⋅ sec/cc; 200 ° C; 16.2 sec

The 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/cc for 16.2 seconds. 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 (CF ₃ C≡CCF ₃ ), 0.0991 mol %. for 1,2,3,3,4,4-hexafluoro-1-cyclobutene (c-C ₄ F ₆ ), below the detection limit (H/O) for 1,1,2,3,3,4,4, 4-octafluoro-1-butene (CF ₂ =CFCF ₂ CF ₃ ) (total E-isomer and Z-isomer), 0.0850 mol %. for 1,1,1,2,4,4,4-heptafluoro-2-butene (CF ₃ CF=CHCF ₃ ) (total E-isomer and Z-isomer) and 0.0159 mol %. for all other by-products.

[0193]

Example 1-11: Chromium oxide catalyst; W/F=30.0 g ⋅ sec/cc; 20 ° C; 25.1 sec

The 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 seconds 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 (CF ₃ C≡CCF ₃ ), below the detection limit (H / O) for 1,2,3,3,4,4-hexafluoro- 1-cyclobutene (c-C ₄ F ₆ ), 0.0257% mol. for 1,1,2,3,3,4,4,4-octafluoro-1-butene (CF ₂ =CFCF ₂ CF ₃ ) (total E-isomer and Z-isomer), 0.0511 mol %. for 1,1,1,2,4,4,4-heptafluoro-2-butene (CF ₃ CF=CHCF ₃ ) (total 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/cc; 20 ° C; 11.7 sec

The reaction is carried out in the same manner as in example 1, except that the reaction is carried out with a W/F ratio of 14.0 g⋅sec/cc at a heating temperature of 20°C for 11.7 seconds using as a catalyst chromium oxide 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 (CF ₃ C≡CCF ₃ ), below the detection limit (H / O) for 1,2,3,3,4,4-hexafluoro- 1-cyclobutene (c-C ₄ F ₆ ), 0.0187% mol. for 1,1,2,3,3,4,4,4-octafluoro-1-butene (CF ₂ =CFCF ₂ CF ₃ ) (total E-isomer and Z-isomer), 0.0544 mol %. for 1,1,1,2,4,4,4-heptafluoro-2-butene (CF ₃ CF=CHCF ₃ ) (total 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/cc; 50 ° C; 25.1 sec

The 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 seconds using a chromium oxide catalyst as a catalyst. One hour after the completion of the reaction, the gas exiting the reaction tube is analyzed by gas chromatography, which shows that the conversion is 100 mol%, and the selectivity for each component is as follows: 99.9 mol%. for 1,1,1,4,4,4-hexafluoro-2-butyne (CF ₃ C≡CCF ₃ ), below the detection limit (H / O) for 1,2,3,3,4,4-hexafluoro- 1-cyclobutene (c-C ₄ F ₆ ), 0.0201% mol. for 1,1,2,3,3,4,4,4-octafluoro-1-butene (CF ₂ =CFCF ₂ CF ₃ ) (total E-isomer and Z-isomer), 0.0387 mol %. for 1,1,1,2,4,4,4-heptafluoro-2-butene (CF ₃ CF=CHCF ₃ ) (total 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/cc; 150 ° C; 5.0 sec

The 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/cc at a heating temperature of 150°C for 5.0 sec using as a chromium oxide 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 (CF ₃ C≡CCF ₃ ), 0.00311 mol %. for 1,2,3,3,4,4-hexafluoro-1-cyclobutene (c-C ₄ F ₆ ), 0.0274 mol%. for 1,1,2,3,3,4,4,4-octafluoro-1-butene (CF ₂ =CFCF ₂ CF ₃ ) (total E-isomer and Z-isomer), 0.0477 mol %. for 1,1,1,2,4,4,4-heptafluoro-2-butene (CF ₃ CF=CHCF ₃ ) (total 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/cc; 150 ° C; 25.1 sec

The 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 seconds 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 (CF ₃ C≡CCF ₃ ), 0.00154 mol %. for 1,2,3,3,4,4-hexafluoro-1-cyclobutene (c-C ₄ F ₆ ), 0.0272 mol%. for 1,1,2,3,3,4,4,4-octafluoro-1-butene (CF ₂ =CFCF ₂ CF ₃ ) (total E-isomer and Z-isomer), 0.0364 mol %. for 1,1,1,2,4,4,4-heptafluoro-2-butene (CF ₃ CF=CHCF ₃ ) (total E-isomer and Z-isomer) and 0.125 mol %. for all other by-products.

[0198]

Example 1-16: Chromium oxide catalyst; W/F=8.0 g⋅sec/cc; 200 ° C; 6.7 sec

The 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 8.0 g⋅sec/cc for 6.7 seconds 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 rate was 99.9 mol % and the selectivity for each component was as follows: 99.6 mol %. for 1,1,1,4,4,4-hexafluoro-2-butyne (CF ₃ C≡CCF ₃ ), 0.00311 mol %. for 1,2,3,3,4,4-hexafluoro-1-cyclobutene (c-C ₄ F ₆ ), below the detection limit (H/O) for 1,1,2,3,3,4,4, 4-octafluoro-1-butene (CF ₂ =CFCF ₂ CF ₃ ) (total E-isomer and Z-isomer), 0.00111 mol %. for 1,1,1,2,4,4,4-heptafluoro-2-butene (CF ₃ CF=CHCF ₃ ) (total 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/cc; 200 ° C; 13.3 sec

The 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/cc for 13.3 seconds using a chromium oxide catalyst as a catalyst. One hour after the completion of the reaction, the gas exiting the reaction tube is analyzed by gas chromatography, which shows that the conversion is 100 mol%, and the selectivity for each component is as follows: 99.9 mol%. for 1,1,1,4,4,4-hexafluoro-2-butyne (CF ₃ C≡CCF ₃ ), 0.00311 mol %. for 1,2,3,3,4,4-hexafluoro-1-cyclobutene (c-C ₄ F ₆ ), below the detection limit (H/O) for 1,1,2,3,3,4,4, 4-octafluoro-1-butene (CF ₂ =CFCF ₂ CF ₃ ) (total E-isomer and Z-isomer), 0.00101 mol %. for 1,1,1,2,4,4,4-heptafluoro-2-butene (CF ₃ CF=CHCF ₃ ) (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/cc; 200 ° C; 11.1 sec

The 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/cc for 11.1 seconds using a titanium 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 rate 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 (CF ₃ C≡CCF ₃ ), 0.254 mol %. for 1,2,3,3,4,4-hexafluoro-1-cyclobutene (c-C ₄ F ₆ ), 0.059 mol%. for 1,1,2,3,3,4,4,4-octafluoro-1-butene (CF ₂ =CFCF ₂ CF ₃ ) (total E-isomer and Z-isomer), 0.0341 mol %. for 1,1,1,2,4,4,4-heptafluoro-2-butene (CF ₃ CF=CHCF ₃ ) (total 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/cc; 200 ° C; 15.5 sec

The 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/cc for 15.5 seconds using a titanium 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 99.0 mole % and the selectivity for each component was as follows: 99.3 mole %. for 1,1,1,4,4,4-hexafluoro-2-butyne (CF ₃ C≡CCF ₃ ), 0.362 mol %. for 1,2,3,3,4,4-hexafluoro-1-cyclobutene (c-C ₄ F ₆ ), 0.0587 mol%. for 1,1,2,3,3,4,4,4-octafluoro-1-butene (CF ₂ =CFCF ₂ CF ₃ ) (total E-isomer and Z-isomer), 0.0321 mol %. for 1,1,1,2,4,4,4-heptafluoro-2-butene (CF ₃ CF=CHCF ₃ ) (total E-isomer and Z-isomer) and 0.247 mol %. for all other by-products.

[0202]

Example 1-20: Aluminosilicate catalyst; W/F=7.5 g⋅sec/cc; 20 ° C; 14.9 sec

The reaction is carried out in the same manner as in Example 1-1, except that the reaction is carried out with a W/F ratio of 7.5 g⋅sec/cc at a heating temperature of 20°C for 14.9 seconds using as an aluminosilicate 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 100 mol % and the selectivity for each component was as follows: 99.4 mol %. for 1,1,1,4,4,4-hexafluoro-2-butyne (CF ₃ C≡CCF ₃ ), below the detection limit (H / O) for 1,2,3,3,4,4-hexafluoro- 1-cyclobutene (c-C ₄ F ₆ ), below the detection limit (H / O) for 1,1,2,3,3,4,4,4-octafluoro-1-butene (CF ₂ \u003d CFCF ₂ CF ₃ ) (total amount of E-isomer and Z-isomer), 0.0909 mol%. for 1,1,1,2,4,4,4-heptafluoro-2-butene (CF ₃ CF=CHCF ₃ ) (total 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/cc; 20 ° C; 29.9 sec

The reaction is carried out in the same manner as in Example 1-1, except that the reaction is carried out with a W/F ratio of 15.0 g⋅sec/cc at a heating temperature of 20°C for 29.9 seconds using as an aluminosilicate catalyst. One hour after the completion of the reaction, the gas exiting the reaction tube is analyzed by gas chromatography, which shows that the conversion is 100 mol%, and the selectivity for each component is as follows: 99.9 mol%. for 1,1,1,4,4,4-hexafluoro-2-butyne (CF ₃ C≡CCF ₃ ), below the detection limit (H / O) for 1,2,3,3,4,4-hexafluoro- 1-cyclobutene (c-C ₄ F ₆ ), 0.00688% mol. for 1,1,2,3,3,4,4,4-octafluoro-1-butene (CF ₂ =CFCF ₂ CF ₃ ) (total E-isomer and Z-isomer), 0.0555 mol %. for 1,1,1,2,4,4,4-heptafluoro-2-butene (CF ₃ CF=CHCF ₃ ) (total 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/cc; 20 ° C; 59.8 sec

The 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 seconds 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: 99.8 mol %. for 1,1,1,4,4,4-hexafluoro-2-butyne (CF ₃ C≡CCF ₃ ), below the detection limit (H / O) for 1,2,3,3,4,4-hexafluoro- 1-cyclobutene (c-C ₄ F ₆ ), below the detection limit (H / O) for 1,1,2,3,3,4,4,4-octafluoro-1-butene (CF ₂ \u003d CFCF ₂ CF ₃ ) (total amount of E-isomer and Z-isomer), 0.0804 mol%. for 1,1,1,2,4,4,4-heptafluoro-2-butene (CF ₃ CF=CHCF ₃ ) (total 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/cc; 100 ° C; 8.0 sec

The reaction is carried out in the same manner as in Example 1, except that the reaction is carried out with a W/F ratio of 4.0 g⋅sec/cc at a heating temperature of 100°C for 8.0 sec using as a catalyst aluminosilicate 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 100 mol % and the selectivity for each component was as follows: 99.4 mol %. for 1,1,1,4,4,4-hexafluoro-2-butyne (CF ₃ C≡CCF ₃ ), 0.00121 mol %. for 1,2,3,3,4,4-hexafluoro-1-cyclobutene (c-C ₄ F ₆ ), below the detection limit (H/O) for 1,1,2,3,3,4,4, 4-octafluoro-1-butene (CF ₂ =CFCF ₂ CF ₃ ) (total E-isomer and Z-isomer), 0.0909 mol %. for 1,1,1,2,4,4,4-heptafluoro-2-butene (CF ₃ CF=CHCF ₃ ) (total E-isomer and Z-isomer) and 0.503 mol %. for all other by-products.

[0206]

Example 1-24: Aluminosilicate catalyst; W/F=4.0 g⋅sec/cc; 200 ° C; 8.0 sec

The 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/cc for 8.0 seconds using an aluminosilicate catalyst as a catalyst. One hour after the completion of the reaction, the gas exiting the reaction tube is analyzed by gas chromatography, which shows that the conversion is 100 mol%, and the selectivity for each component is as follows: 99.5 mol%. for 1,1,1,4,4,4-hexafluoro-2-butyne (CF ₃ C≡CCF ₃ ), 0.0670 mol %. for 1,2,3,3,4,4-hexafluoro-1-cyclobutene (c-C ₄ F ₆ ), below the detection limit (H/O) for 1,1,2,3,3,4,4, 4-octafluoro-1-butene (CF ₂ =CFCF ₂ CF ₃ ) (total E-isomer and Z-isomer), 0.0101 mol %. for 1,1,1,2,4,4,4-heptafluoro-2-butene (CF ₃ CF=CHCF ₃ ) (total 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/cc; 200 ° C; 16.0 sec

The reaction proceeds as in Example 1-1, except that the reaction is carried out with a W/F ratio of 8.0 g⋅sec/cc for 16.0 seconds using an aluminosilicate catalyst as a catalyst. One hour after the completion of the reaction, the gas exiting the reaction tube is analyzed by gas chromatography, which shows that the conversion is 100 mol%, and the selectivity for each component is as follows: 99.5 mol%. for 1,1,1,4,4,4-hexafluoro-2-butyne (CF ₃ C≡CCF ₃ ), 0.0611 mol %. for 1,2,3,3,4,4-hexafluoro-1-cyclobutene (c-C ₄ F ₆ ), below the detection limit (H/O) for 1,1,2,3,3,4,4, 4-octafluoro-1-butene (CF ₂ =CFCF ₂ CF ₃ ) (total E-isomer and Z-isomer), 0.00921 mol %. for 1,1,1,2,4,4,4-heptafluoro-2-butene (CF ₃ CF=CHCF ₃ ) (total 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.

[0209]

table 2

Example 1-1 1-10 1-11 1-12 1-13 1-14 1-15 1-16 1-17 Catalyst Fluorinated chromium oxide Fluorinated chromium oxide Chromium oxide Chromium oxide Chromium oxide Chromium oxide Chromium oxide Chromium oxide Chromium oxide W/F 30.0 15.0 30.0 14.0 30.0 6.0 30.0 8.0 16.0 Temperature (°C) 200 200 twenty twenty fifty 150 150 200 200 Contact time (sec) 23.1 16.2 25.1 11.7 25.1 5.0 25.1 6.7 13.3 Conversion (mol %) 100 100 100 100 100 100 100 99.9 100 Selectivity (mol %) _{CF3 C≡CCF3} 99.7 99.8 99.8 99.8 99.9 99.8 99.8 99.6 99.9 c-C ₄ F ₆ 0.162 0.0991 BUT BUT BUT 0.00311 0.00154 0.00311 0.00311 _{CF2 = CFCF2CF3} 0.0356 BUT 0.0257 0.0187 0.0201 0.0274 0.0272 BUT BUT _CF3 CF= _CHCF3 0.0947 0.0850 0.0511 0.0544 0.0387 0.0477 0.0364 0.00111 0.00101 Other 0.0182 0.0159 0.0832 0.0969 0.0012 0.0818 0.125 0.416 0.0959 Total 100 100 100 100 100 100 100 100 100

[0210]

Table 3

Example 1-18 1-19 1-20 1-21 1-22 1-23 1-24 1-25 Catalyst Titanium dioxide Titanium dioxide Aluminosilicate Aluminosilicate Aluminosilicate Aluminosilicate Aluminosilicate Aluminosilicate W/F 10.0 14.0 7.5 15.0 30.0 4.0 4.0 8.0 Temperature (°C) 200 200 twenty twenty twenty 100 200 200 Contact time (sec) 11.1 15.5 14.9 29.9 59.8 8.0 8.0 16.0 Conversion (mol %) 99.0 99.0 100 100 100 100 100 100 Selectivity (mol %) _{CF3 C≡CCF3} 99.4 99.3 99.4 99.9 99.8 99.4 99.5 99.5 c-C ₄ F ₆ 0.254 0.362 BUT BUT BUT 0.00121 0.0670 0.0611 _{CF2 = CFCF2CF3} 0.059 0.0587 BUT 0.00688 BUT BUT BUT BUT _CF3 CF= _CHCF3 0.0341 0.0321 0.0909 0.0555 0.0804 0.0909 0.0101 0.00921 Other 0.213 0.247 0.504 0.0374 0.161 0.503 0.467 0.480 Total 100 100 100 100 100 100 100 100

[0211]

Example 2 : Requirements (C)-(F)

The following catalysts are used in Example 2 below.

Fluorinated chromium oxide catalyst (1): chromium oxide fluorinated with hydrogen fluoride; porosity 0.10 ml/g; chromium oxide (Cr ₂ O ₃ , porosity 0.15 ml/g) is fluorinated by allowing hydrogen fluoride to pass through at atmospheric pressure at 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 (Cr ₂ O ₃ , porosity 0.15 ml/g) is fluorinated, allowing chlorodifluoromethane (R22) to pass through at atmospheric pressure at 100 to 500°C for 6 hours.

Fluorinated aluminosilicate catalyst (1): aluminosilicate fluorinated with hydrogen fluoride; porosity 0.55 ml/g; the aluminosilicate (porosity 0.70 ml/g) is fluorinated by allowing hydrogen fluoride to pass through at atmospheric pressure at 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, allowing chlorodifluoromethane (R22) to pass through it at atmospheric pressure at a temperature of from 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 at atmospheric pressure at 100 to 400° C. for 6 hours.

Table 4 provides details for fluorinated alumina catalysts.

[0213]

Table 4

Fluorinated alumina catalyst (one) (2) (3) (four) (5) Physical properties before fluorination Specific surface area (m ² /g) 165 300 166 150 270 Porosity (ml/g) 0.91 0.61 0.37 0.51 0.38 Physical properties after fluorination Specific surface area (m ² /g) 97.4 141 84.4 122 93.8 Porosity (ml/g) 1.33 0.43 0.22 0.39 0.23 Composition after fluorination F (% atom) 16.9 18.1 16.9 18.3 48.7

[0214]

Example 2-1 Chromium oxide catalyst fluorinated with R22; Porosity 0.13 ml/g

As a catalyst, the fluorinated chromium oxide catalyst (2) (chromium oxide fluorinated with chlorodifluoromethane (R22)) is loaded into a metal tubular reactor. The reaction tube is heated to 200° C. and hexafluorobutadiene (CF ₂ CF=CFCF ₂ ) is fed into the reaction tube until a W/F ratio of 8 g⋅sec/cc is reached to allow the reaction to proceed in a gas-phase continuous flow process. After a predetermined 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 degradation rate of the catalyst 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.

Table 5 presents the results.

[0215]

Table 5

Fluorinated Chromium Oxide Catalyst Degradation rate: -0.12% Before fluoridation
Porosity: 0.15 ml/g After fluoridation
Porosity: 0.13 ml/g W/F (g⋅sec/cc) eight eight eight eight eight eight eight eight Reaction time one 6 24 29 32 48 51 60 Conversion (mol %) 100 100 100 99.9 99.8 98.1 97.2 96.4 Selectivity (mol %) _{CF3 C≡CCF3} 99.0 99.4 99.4 99.6 99.6 99.6 99.6 99.7 _{CF2 = CFCF2CF3} 0.0609 0.0507 0.0582 0.0541 0.0510 0.0504 0.0441 0.00128 c-C ₄ F ₆ 0.00394 0.000984 0.0442 0.0347 0.0336 0.0775 0.0822 0.0433 _CF3 CF= _CHCF3 0.176 0.198 0.166 0.106 0.110 0.0910 0.0923 0.0902 C ₄ F ₇ H (except for CF ₃ CF=CHCF ₃ ) BUT BUT BUT BUT BUT BUT BUT BUT Other 0.727 0.392 0.295 0.228 0.182 0.213 0.155 0.202 Total 100 100 100 100 100 100 100 100

[0216]

Example 2-2: Aluminosilicate catalyst fluorinated with R22; Porosity 0.69 ml/g

The reaction proceeds as in Example 2-1, except that the fluorinated aluminosilicate catalyst (2) (aluminosilicate fluorinated with chlorodifluoromethane (R22)) is used as a catalyst instead of the fluorinated chromium oxide catalyst (2). After a predetermined period of time, the gas exiting the reaction tube is analyzed by gas chromatography. The results show that the catalyst degradation rate is -0.0014%/hr. The degradation rate of the catalyst 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 6.

[0217]

Table 6

Fluorinated aluminosilicate catalyst Degradation rate: -0.0014% Before fluoridation
Porosity: 0.70 ml/g After fluoridation
Porosity: 0.69 ml/g W/F (g⋅sec/cc) eight eight eight eight eight eight eight eight eight eight Reaction time (hour) 3 19 27 34 51 58 75 78 81 100 Conversion (mol %) 100 100 100 100 100 99.9 99.9 99.8 99.8 99.7 Selectivity (mol %) _{CF3 C≡CCF3} 99.5 99.8 99.7 99.8 99.8 99.8 99.8 99.8 99.8 99.6 _{CF2 = CFCF2CF3} 0.00162 0.00306 0.00402 0.00509 0.00704 0.00529 0.00658 0.00595 0.00653 0.00911 c-C ₄ F ₆ 0.0570 0.0793 0.0966 0.106 0.121 0.117 0.129 0.127 0.128 0.144 _CF3 CF= _CHCF3 0.104 0.00811 0.135 0.0986 0.0872 0.0891 0.0840 0.0816 0.0875 0.290 C ₄ F ₇ H (except CF ₃ CF=CHCF ₃ ) BUT BUT BUT BUT BUT BUT BUT BUT BUT BUT Other 0.386 0.154 0.0346 0.0317 0.000 0.0307 0.000276 0.00203 0.00561 0.00430 Total 100 100 100 100 100 100 100 100 100 100

[0218]

Example 2-3: Fluorinated alumina catalyst; Porosity 1.33 ml/g

The reaction proceeds as in Example 2-1, except that the fluorinated alumina catalyst (1) is used as a catalyst instead of the fluorinated chromium oxide catalyst (2). After a predetermined period of time, the gas exiting the reaction tube is analyzed by gas chromatography. The results show that the catalyst degradation rate is -0.025%/hour. The degradation rate of the catalyst 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 7.

[0219]

Table 7

Fluorinated alumina catalyst Degradation rate: -0.025% Before fluoridation
Porosity 0.91 ml/g After fluoridation
Porosity 1.33 ml/g W/F (g⋅sec/cc) four four four four four Reaction time (hour) 2.4 5.7 21 thirty fifty Conversion (mol %) 100 100 99.9 99.4 97.7 Selectivity (mol %) _{CF3 C≡CCF3} 98.7 99.5 99.5 99.5 99.4 _{CF2 = CFCF2CF3} BUT BUT BUT BUT BUT c-C ₄ F ₆ 0.273 0.300 0.327 0.302 0.358 _CF3 CF= _CHCF3 0.295 0.169 0.110 0.192 0.175 C ₄ F ₇ H (except for CF ₃ CF=CHCF ₃ ) BUT BUT BUT BUT BUT Other 0.703 0.0755 0.0697 0.0465 0.063 Total 100 100 100 100 100

[0220]

Example 2-4: Fluorinated alumina catalyst; Porosity 0.43 ml/g

The reaction proceeds as in Example 2-1, except that the fluorinated alumina catalyst (2) is used as a catalyst instead of the fluorinated chromium oxide catalyst (2). After a predetermined period of time, the gas exiting the reaction tube is analyzed by gas chromatography. The results show that the catalyst degradation rate is -0.026%/hr. The degradation rate of the catalyst 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 8.

[0221]

Table 8

Fluorinated alumina catalyst Degradation rate: -0.026% Before fluoridation
Porosity 0.61 ml/g After fluoridation
Porosity 0.43 ml/g W/F (g⋅sec/cc) four four four four four Reaction time (hour) 1.5 5.0 twenty 27 45 Conversion (mol %) 99.8 99.8 99.6 99.3 97.2 Selectivity (mol %) _{CF3 C≡CCF3} 99.6 99.6 99.6 99.6 99.3 _{CF2 = CFCF2CF3} 0.00104 0.00229 0.00416 0.00400 0.00674 c-C ₄ F ₆ 0.199 0.219 0.244 0.257 0.271 _CF3 CF= _CHCF3 0.128 0.108 0.0927 0.112 0.180 C ₄ F ₇ H (except CF ₃ CF=CHCF ₃ ) BUT BUT BUT BUT BUT Other 0.0823 0.0335 0.0400 0.0468 0.255 Total 100 100 100 100 100

[0222]

Comparative Example 2-1: Fluorinated alumina catalyst; Porosity 0.22 ml/g

The reaction proceeds as in Example 2-1, except that the fluorinated alumina catalyst (3) is used as a catalyst instead of the fluorinated chromium oxide catalyst (2). After a predetermined period of time, the gas exiting the reaction tube is analyzed by gas chromatography. The results show that the catalyst degradation rate is -0.65%/hr. The degradation rate of the catalyst 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 9.

[0223]

Table 9

Fluorinated alumina catalyst Degradation rate: -0.65% Before fluoridation
Porosity 0.37 ml/g After fluoridation
Porosity 0.22 ml/g W/F (g⋅sec/cc) four four four Reaction (hour) 2.4 5.8 ten Conversion (mol %) 99.5 97.2 94.3 Selectivity (mol %) _{CF3 C≡CCF3} 99.5 99.3 99.6 _{CF2 = CFCF2CF3} BUT BUT BUT c-C ₄ F ₆ 0.214 0.230 0.0247 _CF3 CF= _CHCF3 0.160 0.410 0.116 C ₄ F ₇ H (except CF ₃ CF=CHCF ₃ ) BUT BUT BUT Other 0.104 0.0496 0.263 Total 100 100 100

[0224]

Example 2-5: Fluorinated alumina catalyst; Porosity 0.39 ml/g

The reaction proceeds as in Example 2-1, except that the fluorinated alumina catalyst (4) is used as a catalyst instead of the fluorinated chromium oxide catalyst (2). After a predetermined period of time, the gas exiting the reaction tube is analyzed by gas chromatography. The results show that the catalyst degradation rate is -0.29%/hour. The degradation rate of the catalyst 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 10.

[0225]

Table 10

Fluorinated alumina catalyst Degradation rate: -0.29% Before fluoridation
Porosity 0.51 ml/g After fluoridation
Porosity 0.39 ml/g W/F (g⋅sec/cc) four four four Reaction time (hour) ten 28 47 Conversion (mol %) 100 94.3 88.2 Selectivity (mol %) _{CF3 C≡CCF3} 99.8 99.7 99.6 _{CF2 = CFCF2CF3} 0.00688 0.00612 0.00987 c-C ₄ F ₆ 0.198 0.217 0.241 _CF3 CF= _CHCF3 0.00702 0.104 0.097 C ₄ F ₇ H (except CF ₃ CF=CHCF ₃ ) 0.00806 BUT BUT Other 0.00123 0.000386 0.00942 Total 100 100 100

[0226]

Comparative Example 2-2: Fluorinated alumina catalyst; Porosity 0.23 ml/g

The reaction proceeds as in Example 2-1, except that the fluorinated alumina catalyst (5) is used as a catalyst instead of the fluorinated chromium oxide catalyst (2). After a predetermined period of time, the gas exiting the reaction tube is analyzed by gas chromatography. The results show that the catalyst degradation rate is -0.67%/hr. The degradation rate of the catalyst 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 11.

[0227]

Table 11

Fluorinated alumina catalyst Degradation rate: -0.67% Before fluoridation
Porosity 0.38 ml/g After fluoridation
Porosity 0.23 ml/g W/F (g⋅sec/cc) four four four Reaction time (hour) 1.0 fifteen twenty Conversion (mol %) 99.7 93.3 83.9 Selectivity (mol %) _{CF3 C≡CCF3} 99.6 99.5 99.1 _{CF2 = CFCF2CF3} 0.00303 0.00488 0.00426 c-C ₄ F ₆ 0.142 0.234 0.302 _CF3 CF= _CHCF3 0.115 0.218 0.127 C ₄ F ₇ H (except CF ₃ CF=CHCF ₃ ) BUT BUT BUT Other 0.132 0.0511 0.437 Total 100 100 100

[0228]

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

[0229]

Example 3: Requirement (G)

Example 3 below uses a chromium oxide catalyst (Cr ₂ O ₃ ) or an alumina catalyst (Al ₂ O ₃ ) as a catalyst.

[0230]

The water content of the hexafluorobutadiene is controlled by adding water or by dehydrating with molecular sieves to provide the desired water content. The water content is measured by the Karl-Fischer method.

[0231]

Example 3-1: Chromium oxide catalyst; Water content 20 ppm

The metal tubular reactor is filled with nitrogen to create a nitrogen atmosphere, and then a chromium oxide catalyst is fed as a catalyst. The reaction tube is heated to 200° C. and hexafluorobutadiene (CF ₂ CF=CFCF ₂ ) is fed into the reaction tube until a W/F ratio of 8 g⋅sec/cc is reached to allow the reaction to proceed in a gas-phase continuous flow process. The water content of the hexafluorobutadiene at the beginning of the reaction is 20 ppm by mass, and the water content of the reaction system from the beginning to the end of the reaction is adjusted to 20 ppm. After a predetermined 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%/hr. The degradation rate of the catalyst 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.

[0232]

Table 12

Chromium oxide catalyst Water content 20 ppm Degradation rate: -0.12% Reaction time (hour) 2.21 7.21 21.8 27.0 48.4 52.5 60.1 67.0 Conversion (mol %) 100 100 100 99.9 99.8 98.1 97.1 96.4 Selectivity (mol %) _{CF3 C≡CCF3} 99.0 99.3 99.4 99.6 99.6 99.6 99.6 99.7 _{CF2 = CFCF2CF3} 0.0609 0.0507 0.0582 0.0541 0.0510 0.0504 0.0441 0.00128 c-C ₄ F ₆ 0.00394 0.000984 0.0442 0.0347 0.0336 0.0775 0.0822 0.0433 _CF3 CF= _CHCF3 0.176 0.198 0.166 0.106 0.110 0.0910 0.0923 0.0902 C ₄ F ₇ H (except CF ₃ CF=CHCF ₃ ) BUT BUT BUT BUT BUT BUT BUT BUT Other 0.727 0.492 0.295 0.228 0.182 0.213 0.155 0.192 Total 100 100 100 100 100 100 100 100

[0233]

Example 3-2: Chromium oxide catalyst; Water content 2 ppm

The reaction proceeds as in Example 3-1, except that the water content of the reaction system from the beginning to the end of the reaction is adjusted to 2 ppm using hexafluorobutadiene with a water content of 2 ppm at the beginning of the reaction instead of hexafluorobutadiene with a water content of 20 mass/million at the beginning of the reaction. After a predetermined 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 degradation rate of the catalyst 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 13.

[0234]

Table 13

Chromium oxide catalyst Water content 2 ppm Degradation rate: -0.12% Reaction time (hour) 1.21 6.42 24.4 29.0 31.5 48.2 51.4 60.0 Conversion (mol %) 100 100 100 99.9 99.8 98.1 97.2 96.4 Selectivity (mol %) _{CF3 C≡CCF3} 99.0 99.4 99.5 99.6 99.6 99.6 99.6 99.7 _{CF2 = CFCF2CF3} 0.0609 0.0507 0.0582 0.0541 0.0510 0.0504 0.0441 0.0013 c-C ₄ F ₆ 0.00394 0.000984 0.0442 0.0347 0.0336 0.0775 0.0822 0.0433 _CF3 CF= _CHCF3 0.176 0.198 0.166 0.106 0.110 0.0910 0.0923 0.0902 C ₄ F ₇ H (except CF ₃ CF=CHCF ₃ ) BUT BUT BUT BUT BUT BUT BUT BUT Other 0.727 0.392 0.275 0.228 0.182 0.213 0.155 0.202 Total 100 100 100 100 100 100 100 100

[0235]

Example 3-3: Alumina Catalyst; Water content 20 ppm

The reaction proceeds as in Example 3-1, except that an alumina catalyst is used instead of a chromium oxide catalyst. After a predetermined period of time, the gas exiting the reaction tube is analyzed by gas chromatography. The results show that the catalyst degradation rate is -0.0302%/hr. The degradation rate of the catalyst 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 14.

[0236]

Table 14

alumina catalyst Water content 20 ppm Degradation rate: -0.0302% Reaction time (hour) 10.2 16.3 34.1 Conversion (mol %) 100 99.7 99.2 Selectivity (mol %) _{CF3 C≡CCF3} 99.6 99.6 99.7 _{CF2 = CFCF2CF3} BUT 0.00101 0.00611 c-C ₄ F ₆ 0.204 0.215 0.219 _CF3 CF= _CHCF3 0.161 0.129 0.103 C ₄ F ₇ H (except CF ₃ CF=CHCF ₃ ) 0.0120 BUT BUT Other 0.00540 0.0163 0.000435 Total 100 100 100

[0237]

Example 3-4: Alumina Catalyst; Water content 2 ppm

The reaction proceeds as in Example 3-1, except that an alumina catalyst is used instead of a chromium oxide catalyst and that the water content of the reaction system is adjusted to 2 ppm from start to finish by using hexafluorobutadiene with a water content of 2 mass/million at the beginning of the reaction instead of hexafluorobutadiene with a water content of 20 mass/million at the beginning of the reaction. After a predetermined period of time, the gas exiting the reaction tube is analyzed by gas chromatography. The results show that the catalyst degradation rate is -0.08%/hr. The degradation rate of the catalyst 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 15.

[0238]

Table 15

alumina catalyst Water content 2 ppm Degradation rate: -0.08% Reaction time (hour) 9.02 15.2 32.3 Conversion (mol %) 100 99.7 99.2 Selectivity (mol %) _{CF3 C≡CCF3} 99.6 99.6 99.7 _{CF2 = CFCF2CF3} BUT 0.00009 0.0070 c-C ₄ F ₆ 0.204 0.215 0.219 _CF3 CF= _CHCF3 0.161 0.129 0.100 C ₄ F ₇ H (except CF ₃ CF=CHCF ₃ ) 0.0120 BUT BUT Other 0.00540 0.0173 0.00254 Total 100 100 100

Claims (30)

1. A process for producing a perfluoroalkyne compound, comprising reacting a perfluoroalkadiene compound in the presence of a catalyst to obtain 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 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; (D) the catalyst contains a fluorinated metal oxide selected from the group consisting of fluorinated alumina and fluorinated aluminosilicate having a porosity of 0.35 ml/g or more; (E) the catalyst contains a metal oxide fluorinated by reacting the metal oxide with at least one compound selected from the group consisting of hydrofluorocarbon, hydrochlorofluorocarbon and chlorofluorocarbon, where the metal oxide metal is at least one element selected from the group including chromium, titanium, silicon and zirconium; and (F) the catalyst comprises one or more catalysts obtained by fluorination of at least one metal oxide selected from the group consisting of chromium oxide having a porosity of 0.10 ml/g or more, alumina having a porosity of 0.45 ml/g, or more, and an aluminosilicate having a porosity of 0.50 ml/g or more. 2. The production method according to claim 1, wherein the perfluoroalkyne compound is represented by the formula (1): CR ¹ ₂ R 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. 3. The production method according to claim 1 or 2, wherein the perfluoroalkadiene compound is represented by the 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 paragraphs. 1-3, wherein the method satisfies condition (E) and the metal oxide before fluorination has a porosity of 0.45 ml/g or more. 5. The production method according to any one of paragraphs. 1-4, wherein the reaction of the perfluoroalkadiene compound is carried out in the gas phase. 6. The production method according to any one of paragraphs. 1-5, wherein the reaction of the perfluoroalkadiene compound is carried out at a temperature of 170°C or higher. 7. The production method according to any one of paragraphs. 1-6, wherein the reaction of the perfluoroalkadiene compound yields the perfluorocycloalkene compound in addition to the perfluoroalkyne compound. 8. The production method according to claim 7, wherein the perfluorocycloalkene compound is represented by the formula (3):

, where the substituents R ¹ -R ⁴ have the meanings defined above. 9. A method for producing a perfluoroalkyne compound, comprising obtaining a perfluoroalkadiene compound using, as a substrate, a perfluorocycloalkene compound obtained as a by-product in the production method according to claim 7 or 8. 10. The production method according to claim 9, wherein the perfluoroalkyne compound is represented by the formula (1): CR ¹ ₂ R 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. 11. A catalyst for use in the reaction of a perfluoroalkadiene compound to produce a perfluoroalkyne compound, 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 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; (D) the catalyst contains a fluorinated metal oxide selected from the group consisting of fluorinated alumina and fluorinated aluminosilicate having a porosity of 0.35 ml/g or more. 12. A method for producing a catalyst for use in the reaction of a perfluoroalkadiene compound to produce a perfluoroalkyne compound, comprising the following step (E) or (F): (E) reacting the metal oxide with at least one compound selected from the group consisting of hydrofluorocarbon, hydrochlorofluorocarbon and chlorofluorocarbon to thereby fluorinate the metal oxide, wherein the metal oxide metal is at least one element selected from the group consisting of chromium, titanium, silicon and zirconium; (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, alumina having a porosity of 0.45 ml/g or more, and aluminosilicate having a porosity of 0 .50 ml/g or more. 13. The production method according to claim 12, wherein the method satisfies condition (E) and the metal oxide before fluorination has a porosity of 0.45 ml/g or more.

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