JP2007320874A - Method for producing perfluoroalkyne compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for efficiently producing perfluoroalkyne compound in high yield through a gas phase circulation system with industrial advantage. <P>SOLUTION: In this production method, a dihydrohalogenoalkane compound represented by formula (1) [R<SP>1</SP>-CHA-CHB-R<SP>2</SP>] and/or a monohydrohalogenoalkene compound represented by formula (2) [R<SP>1</SP>-CH=CX-R<SP>2</SP>](wherein R<SP>1</SP>and R<SP>2</SP>are each independently a 1-6C perfluoroalkyl group wherein R<SP>1</SP>and R<SP>2</SP>may bond to each other to form a ring; in formula 1, A and B are each independently a halogen atom selected from the group consisting of F, Cl, Br and I; in formula 2, X is a halogen atom selected from the group consisting of F, Cl, Br, and I) is allowed to react in the presence of a metal halide at a reaction temperature equal to or higher than 500°C through the gas phase circulation system. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

The present invention relates to a plasma reaction gas used in the field of manufacturing semiconductor devices, a monomer that is a raw material of a fluorine-containing polymer, and a method for producing a perfluoroalkyne compound useful as a fluorine-containing pharmaceutical intermediate.

A perfluoroalkyne compound is a hydrocarbon compound in which a hydrogen atom is completely substituted with a fluorine atom and has a carbon-carbon triple bond, and is used in a raw material for producing a fluorine-containing polymer, a medical and agrochemical, and a semiconductor production process. It is useful as a plasma reaction gas. In particular, a perfluoroalkyne compound having a relatively low molecular weight such as perfluoro-2-pentyne has an appropriate boiling point and is easy to handle, and thus has high utility value, and establishment of an industrial production method is demanded.

Patent Document 1 discloses a method for obtaining a perfluoroalkyne by reacting a dihydrohalogenoalkane compound and / or a monohydrohalogenoalkene compound in the presence of zeolite at a reaction temperature of 200 ° C. or 250 ° C. in a gas phase flow system. ing.

On the other hand, Patent Document 2 describes a method for producing 1-fluorocyclohexene using 1-difluorocyclohexane as a raw material and a metal fluoride as a dehydrofluorination catalyst, but the reaction temperature is 500 ° C. or lower. No alkyne compound has been obtained.
JP 2004-292329 A Japanese Examined Patent Publication No. 7-100673

However, when the vapor phase distribution method is applied to the manufacturing method disclosed in Patent Document 1, there is still an insufficient aspect in terms of perfluoroalkyne production efficiency. Accordingly, an object of the present invention is to provide a method for efficiently producing a perfluoroalkyne compound in a high yield by a gas phase distribution method.

The inventors of the present invention have made extensive studies to achieve the above object,
Using metal fluoride,
It has been found that by setting the reaction temperature to a specific temperature or higher, the perfluoroalkyne compound can be obtained in a high yield and high efficiency by the vapor phase flow method, and the present invention has been completed.

That is, the present invention relates to a dihydrohalogenoalkane compound (formula 1) and / or a monohydrohalogenoalkene compound (formula 2) represented by the following formula in the vapor phase distribution at a reaction temperature of 500 ° C. or higher in the presence of a metal fluoride. Provided is a method for producing a perfluoroalkyne compound characterized by reacting with the formula.
R ¹ —CHA—CHB—R ² (Formula 1)
R ¹ —CH═CX—R ² (Formula 2)
(In Formulas 1 and 2, R ¹ and R ² are each independently a perfluoroalkyl group having 1 to 6 carbon atoms, and R ¹ and R ² may combine to form a ring. In formula 1, A and B are each independently one halogen atom selected from the group consisting of F, Cl, Br and I. In formula 2, X is from the group consisting of F, Cl, Br and I. One kind of halogen atom selected.)

The metal fluoride is preferably supported on a carrier having a specific surface area measured by the BET method of 100 m ² / g or more.

Further, in the above formula, it is desirable that R ¹ is a perfluoromethyl group, R ² is a perfluoroethyl group, and the perfluoroalkyne compound is perfluoro-2-pentyne.

According to the present invention, a gas for plasma reaction used in the field of manufacturing semiconductor devices, a monomer as a raw material for a fluorine-containing polymer, and a perfluoroalkyne compound useful as a fluorine-containing pharmaceutical intermediate can be produced efficiently in a high yield. can do.

In the method for producing a perfluoroalkyne compound of the present invention, a dihydrohalogenoalkane compound (formula 1) and / or a monohydrohalogenoalkene compound (formula 2) represented by the following formula is reacted with a reaction temperature of 500 in the presence of a metal fluoride. It is characterized by reacting in a vapor-phase flow type at a temperature of not lower than ° C.
R ¹ —CHA—CHB—R ² (Formula 1)
R ¹ —CH═CX—R ² (Formula 2)
(In Formulas 1 and 2, R ¹ and R ² are each independently a perfluoroalkyl group having 1 to 6 carbon atoms, and R ¹ and R ² may combine to form a ring. In formula 1, A and B are each independently one halogen atom selected from the group consisting of F, Cl, Br and I. In formula 2, X is from the group consisting of F, Cl, Br and I. One kind of halogen atom selected.)

In the present invention, when the raw material is a dihydrohalogenoalkane compound (formula 1), a monohydrohalogenoalkene compound (formula 2 ′) is first produced, and this further reacts to produce a perfluoroalkyne compound (formula 3). Generate.
R ¹ —CHA—CHB—R ² (Formula 1)
(In Formula 1, R ¹ and R ² are each independently a C 1-6 perfluoroalkyl group, and R ¹ and R ² may combine to form a ring. , A and B are each independently one halogen atom selected from the group consisting of F, Cl, Br and I.)
R ¹ -CY = CZ-R ² (Formula 2 ′)
(Wherein 2 ', ^{R 1} and ^{R 2,} .Y / Z B include hydrogen atoms / wherein 1 represents the same meaning as ^{R 1} and ^{R 2} in Formula 1 or,, A / hydrogen in Formula 1 Represents an atom.)
R ¹ —C≡C—R ² (Formula 3)
(In the formula 3, ^{R 1} and ^{R 2} have the same meanings as ^{R 1} and ^{R 2} in Formula 1.)

R ¹ and R ² are each independently a perfluoroalkyl group having 1 to 6 carbon atoms, and may be linear (straight and branched) or cyclic. R ¹ and R ² may be combined to form a ring. In such a case, R ¹ and R ² together form a perfluoroalkylene group.

Examples of the linear perfluoroalkyl group include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, and an n group in which a hydrogen atom is completely substituted with a fluorine atom (perfluorination). -Hexyl group; and the like. Examples of the branched perfluoroalkyl group include perfluorinated isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, isopentyl group, sec-pentyl group, tert-pentyl group, and isohexyl group; Is mentioned. Examples of the cyclic perfluoroalkyl group include perfluorinated cyclobutyl group, cyclopentyl group, and cyclohexyl group. Examples of the perfluoroalkylene group include perfluorinated 1,6-hexene group, 1,7-heptene group, 1,8-octene group, and 1,9-nonene group.

The combination of R ¹ and R ² is not particularly limited, but ^two combinations of the same or different groups selected from the group consisting of a perfluoromethyl group, a perfluoroethyl group and a perfluoropropyl group are preferable. More preferably, it is a combination of a perfluoromethyl group and a perfluoroethyl group.

As a specific example of the dihydrohalogenoalkane compound (formula 1),
1,1,1,2,3,4,4,5,5,5-decafluoropentane (In the formula 1, ^{R 1:} perfluoro methyl group, ^{R 2:} perfluoroethyl group, A: F, B: F)
And 1,1,1,2,3,4,4,5,5,6,6,6-dodecafluorohexane (in formula 1, R ¹ : perfluoromethyl group, R ² : perfluorobutyl group, A : F, B: F),
And so on.

Specific examples of monohydrohalogenoalkene compounds (formula 2) include
1,1,1,2,4,4,5,5,5-nonafluoro-2-pentene (in formula 2, R ^{1 is a} perfluoroethyl group, R ^{2 is a} perfluoromethyl group, and X is F) ,
1,1,1,3,4,4,5,5,5-nonafluoro-2-pentene (in formula 2, R ^{1 is a} perfluoromethyl group, R ^{2 is a} perfluoroethyl group, and X is F) ,
1,1,1,2,4,4,5,5,6,6,6-undecafluoro-2-hexene (in formula 2, R ¹ : perfluorobutyl group, R ² : perfluoromethyl group, X: F),
And 1,1,1,3,4,5,5,6,6,6-undecafluoro-2-hexene (in formula 2, R ¹ : perfluoromethyl group, R ² : perfluorobutyl group) , X: F),
And so on.

As the dihydrohalogenoalkane compound (formula 1),
1,1,1,2,3,4,4,5,5,5-decafluoropentane (in formula 1, R ¹ : perfluoromethyl group, R ² : perfluoroethyl group, A: F, B: F)
However, as the monohydrohalogenoalkene compound (formula 2),
1,1,1,2,4,4,5,5,5-nonafluoro-2-pentene (in formula 2, R ^{1 is a} perfluoroethyl group, R ^{2 is a} perfluoromethyl group, and X is F) ,
Alternatively, 1,1,1,3,4,4,5,5,5-nonafluoro-2-pentene (in formula 2, R ^{1 is a} perfluoromethyl group, R ^{2 is a} perfluoroethyl group, and X is F) is there)
Is particularly preferred.

The method for obtaining the dihydrohalogenoalkane compound (Formula 1) is not particularly limited, and a commercially available product may be used, or it may be produced by a known method. For example, the 1,1,1,2,3,4,4,5,5,5-decafluoropentane described above synthesizes perfluoro-2-pentene by addition reaction of tetrafluoroethylene and hexafluoropropylene. However, it can be easily produced by hydrogenating it.

The method for obtaining the monohydrohalogenoalkene compound (Formula 2) is not particularly limited, and a commercially available product may be used, or it may be produced by a known method. For example, means such as synthesis by adding an alkyl halide represented by R ^b -Q to a terminal alkyne compound represented by R ^a C≡CH in the presence of heat, light, or a radical initiator can be applied. (R ^a and R ^b represent a perfluoroalkyl group, and Q represents one halogen atom selected from the group consisting of Cl, Br, and I.)

Each of the dihydrohalogenoalkane compound (formula 1) and the monohydrohalogenoalkene compound (formula 2) may be used alone or in combination of two or more depending on the intended use of the perfluoroalkyne compound. Also good. In addition, both of the dihydrohalogenoalkane compound (formula 1) and the monohydrohalogenoalkene compound (formula 2) may be mixed and used, and the mixing ratio thereof is not particularly limited.

In the present invention, a dihydrohalogenoalkane compound (formula 1) and / or a monohydrohalogenoalkene compound (formula 2) is reacted in a gas-phase flow system at a reaction temperature of 500 ° C. in the presence of a metal fluoride.

The metal fluoride is not particularly limited. For example, alkali metal fluorides such as lithium fluoride, sodium fluoride, potassium fluoride, rubidium fluoride, and cesium fluoride; magnesium fluoride, calcium fluoride, strontium fluoride, And alkaline earth metal fluorides such as barium fluoride; transition metal fluorides such as iron (II) fluoride, iron (III) fluoride, cobalt (II) fluoride, cobalt (III) fluoride, and nickel fluoride Among these, alkali metal fluorides and alkaline earth metal fluorides are preferable, alkali metal fluorides are more preferable, and potassium fluoride and cesium fluoride are more preferable.

These metal fluorides may be used individually by 1 type, and may use 2 or more types together.

Although the metal fluoride may be used as a catalyst as it is, it is preferable that the metal fluoride is supported on a support such as silica, alumina, titania, zirconia, glass, stainless steel, activated carbon, and diatomaceous earth (hereinafter referred to as metal fluoride). Used as a compound-supported catalyst). These carriers may be a crushed material, a molded body processed into an appropriate shape, or a natural material. The shape is preferably a granular shape such as a powder shape, a spherical shape, or a pellet shape.

Carrier for use in the present invention has a specific surface area measured by the BET method is at 100 m ² / g or more, 500 meters ² / g or more is preferable. If the specific surface area is too small, the yield tends to decrease. Moreover, although an upper limit is not limited, in the support | carrier normally used, it is 5,000 m < ² > / g.

The supporting method is not particularly limited, but an impregnation method can be suitably used. For example, it can be supported by dissolving a metal fluoride to be supported in ion-exchanged water, impregnating this aqueous solution into a carrier, and heating to a temperature of 100 to 600 ° C. in an inert gas to remove the ion-exchanged water. it can.

In the reaction in the present invention, when the reaction temperature is less than 500 ° C., a perfluoroalkyne compound is not substantially formed. Therefore, the reaction temperature is 500 ° C. or higher, and from the viewpoint of the corrosion resistance of the reaction base material and the heat stability of the prepared catalyst, 500 to 800 ° C. is preferable, and 550 to 750 ° C. is more preferable.

In addition, when the dihydrohalogenoalkane compound (Formula 1) is used as a raw material, the reaction from the compound to the monohydrohalogenoalkene compound (Formula 2) can proceed even when the reaction temperature is less than 500 ° C. Therefore, when only the dihydrohalogenoalkane compound (formula 1) is used as a starting material, the reaction is initially carried out at a reaction temperature of less than 500 ° C., and the production of a sufficient amount of monohydrohalogenoalkene compound (formula 2) was confirmed. In this stage, the reaction temperature may be 500 ° C. or higher to continue the reaction to produce a desired perfluoroalkyne compound.

The pressure during the reaction is usually normal pressure (0.1 MPa) to 5 MPa, preferably normal pressure to 2 MPa.

In the present invention, the perfluoroalkyne compound is produced by a gas-phase flow type reaction in which the raw material is gasified and passed through a catalyst (metal fluoride or metal fluoride-supported catalyst) layer. A fixed bed reactor or the like is used as the reactor. The material of the reactor is not particularly limited, but usually stainless steel or Hastelloy is used.

The number of reactors is not necessarily one, and a plurality of reactors may be used in series or in parallel.

When the gasified raw material is introduced into the reactor, an inert gas such as helium, nitrogen, or argon may be accompanied if desired.

The gas space velocity based on the cylinder in the reaction (hereinafter abbreviated as “GHSV”) is not particularly limited and is usually 0.1 to 10,000 / hr. 000 to 3,000 / hr is preferable.

In the present invention, the metal fluoride itself is not substantially consumed, and a reaction mixture of the target perfluoroalkyne compound and the by-product hydrogen halide is obtained from the outlet of the reactor.

The post-treatment method and purification method of the reaction mixture are not particularly limited, and known methods are applied. For example, the gaseous reaction mixture coming out of the reactor is brought into contact with a basic compound to neutralize hydrogen halide, and then cooled to a condenser cooled with a refrigerant such as dry ice-acetone or dry ice-ethanol. By collecting and distilling the condensate, the target perfluoroalkyne compound can be purified.
Moreover, it is also possible to refine | purify a target object by removing impurities, such as a water | moisture content, from a condensate using a general desiccant and adsorption agent. Any one of distillation, drying, and adsorption may be performed continuously. When performing continuously, either order may be first.

The perfluoroalkyne compound obtained by the production method of the present invention is a compound represented by the above formula 3, for example, perfluoro-2-butyne, perfluoro-2-pentyne, perfluoro-2-hexyne, perfluoro- Examples include 3-hexyne, perfluoro-2-heptin, and perfluoro-3-heptin.

Among these perfluoroalkyne compounds, perfluoro-2-pentyne is preferably produced by the method of the present invention. The boiling point of the compound is 5 ° C., and it is useful as a raw material for producing fluorine-containing polymers, medical and agricultural chemicals, and gas for plasma reaction.

EXAMPLES The present invention will be specifically described below with reference to examples, but the scope of the present invention is not limited by these examples. Unless otherwise specified, “parts” in Examples and Comparative Examples means “parts by weight”. The reaction product was analyzed by gas chromatography (apparatus: Agilent 6890 manufactured by Agilent Technologies, column: Ultra ALLOY + -1 (s) manufactured by Frontier LAB).

<Method for preparing metal fluoride-supported catalyst (20 wt%)>
In each example and comparative example, the metal fluoride supported catalyst was prepared as follows. 10 g of metal fluoride was dissolved in 10 g of ion exchange water. This aqueous solution was added to 40 g of activated carbon (“granular white ginger G2X 7/12” manufactured by Takeda Pharmaceutical Co., Ltd., specific surface area (BET method) 1,150 m ² / g), and after shaking well, the solution was left for about 1 hour. By this standing, all aqueous solutions were adsorbed on the activated carbon. The activated carbon impregnated with this aqueous solution is filled into a tubular furnace and calcined at 100 ° C. for 1 hour and then at 250 ° C. for 1 hour while circulating nitrogen, and a metal fluoride supported catalyst having a metal fluoride content of 20% by weight is obtained. Prepared.

<Mixture of 1,1,1,2,4,4,5,5,5-nonafluoro-2-pentene and 1,1,1,3,4,4,5,5,5-nonafluoro-2-pentene Synthesis method>
In each example and comparative example, 1,1,1,2,4,4,5,5,5-nonafluoro-2-pentene and 1,1,1,3,4,4,5,5,5- A mixture of nonafluoro-2-pentene was prepared as follows. 118 g potassium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd., purity 85%) and 105 ml of ion-exchanged water were dissolved in a 1 L four-necked flask equipped with a Dimroth cooler and a three-one motor. In an ice bath, 300 g of 1,1,1,2,3,4,4,5,5,5-decafluoropentane (Mitsui DuPont Fluorochemical Co., Ltd.) was added, and then tetraethylammonium bromide (Wako Pure Chemical Industries, Ltd.) 1.0 g) was added, and the mixture was stirred and reacted at 0 ° C. for 4 hours. After confirming the product concentration by gas chromatography, the organic layer was taken out by liquid separation operation. The target product was synthesized by rectifying the organic layer.

Example 1
<Reaction of 1,1,1,2,3,4,4,5,5,5-decafluoropentane (600 ° C.) using a cesium fluoride supported catalyst>
7.6 g of a cesium fluoride-supported catalyst (20% by weight) in which 20% by weight of cesium fluoride (made by Wako Pure Chemical Industries, Ltd.) was supported on activated carbon was placed on a Hastelloy reaction tube (diameter 12.7 mm, length 200 mm). Filled. The reaction tube was set in an electric furnace and heated to 600 ° C. 1,1,1,2,3,4,4,5,5,5-decafluoropentane (manufactured by Mitsui DuPont Fluorochemical Co., Ltd.) was supplied into the vaporizer at a rate of 2.0 g per minute, and vaporized. Feeding was performed at a constant rate for 2 hours from the bottom of the reaction tube.
The gaseous mixture coming out of the reaction tube was fed in the order of aqueous potassium hydroxide and potassium fluoride pellets to neutralize the generated hydrogen fluoride, and then collected in a condenser cooled with dry ice-ethanol. The product was collected in an aqueous potassium hydroxide solution and in a condenser. When the yield of perfluoro-2-pentyne was calculated from the weight of both and gas chromatography analysis results, it was 34.8 mol%. The reaction was carried out at normal pressure, and the gas space velocity “GHSV” was 2527 / hr.

(Example 2)
<Reaction of 1,1,1,2,3,4,4,5,5,5-decafluoropentane (600 ° C.) using a potassium fluoride supported catalyst>
5.4 g of a potassium fluoride-supported catalyst (20% by weight) in which 20% by weight of potassium fluoride (manufactured by Wako Pure Chemical Industries, Ltd.) is supported on activated carbon is placed in a Hastelloy reaction tube (diameter 12.7 mm, length 200 mm). Filled. The reaction tube was set in an electric furnace and heated to 600 ° C. 1,1,1,2,3,4,4,5,5,5-decafluoropentane (manufactured by Mitsui DuPont Fluorochemical) is supplied into the vaporizer at a rate of 1.6 g / min to vaporize the reaction tube. Feeding from the bottom at a constant rate for 2 hours.
The gaseous mixture coming out of the reaction tube was fed in the order of aqueous potassium hydroxide and potassium fluoride pellets to neutralize the generated hydrogen fluoride, and then collected in a condenser cooled with dry ice-ethanol. The product was collected in an aqueous potassium hydroxide solution and in a condenser. The yield of perfluoro-2-pentyne was calculated from the weight of both and gas chromatographic analysis results. As a result, it was 25.0 mol%. The reaction was carried out at normal pressure, and the gas space velocity “GHSV” was 2157 / hr.

(Example 3)
<1,1,1,2,4,4,5,5,5-nonafluoro-2-pentene and 1,1,1,3,4,4,5,5,5 using cesium fluoride supported catalyst -Reaction of a mixture of nonafluoro-2-pentene (600 ° C)>
7.7 g of a cesium fluoride-supported catalyst (20 wt%) in which 20 wt% of cesium fluoride (manufactured by Wako Pure Chemical Industries, Ltd.) is supported on activated carbon is placed in a Hastelloy reaction tube (diameter 12.7 mm, length 200 mm). Filled. The reaction tube was set in an electric furnace and heated to 600 ° C. A mixture of 1,1,1,2,4,4,5,5,5-nonafluoro-2-pentene and 1,1,1,3,4,4,5,5,5-nonafluoro-2-pentene The gas was supplied to the vaporizer at a rate of 1.5 g / min for vaporization, and fed from the bottom of the reaction tube at a constant rate for 1.2 hours.
The gaseous mixture coming out of the reaction tube was fed in the order of aqueous potassium hydroxide and potassium fluoride pellets to neutralize the generated hydrogen fluoride, and then collected in a condenser cooled with dry ice-ethanol. The product was collected in an aqueous potassium hydroxide solution and in a condenser. When the yield of perfluoro-2-pentyne was calculated from the weight of both and gas chromatographic analysis results, it was 46.0 mol%. The reaction was carried out at normal pressure, and the gas space velocity “GHSV” was 2244 / hr.

(Comparative Example 1)
<Reaction of 1,1,1,2,3,4,4,5,5,5-decafluoropentane (400 ° C.) using a cesium fluoride supported catalyst>
7.4 g of a cesium fluoride-supported catalyst (20 wt%) in which 20 wt% of cesium fluoride (manufactured by Wako Pure Chemical Industries, Ltd.) is supported on activated carbon is placed in a Hastelloy reaction tube (diameter 12.7 mm, length 200 mm). Filled. The reaction tube was set in an electric furnace and heated to 400 ° C. 1,1,1,2,3,4,4,5,5,5-decafluoropentane (manufactured by Mitsui DuPont Fluorochemical) was supplied into the vaporizer at a rate of 0.89 g / min to vaporize the reaction tube Feeding from the bottom at a constant speed for 1 hour.
The gaseous mixture coming out of the reaction tube was fed in the order of aqueous potassium hydroxide and potassium fluoride pellets to neutralize the generated hydrogen fluoride, and then collected in a condenser cooled with dry ice-ethanol. The product was collected in an aqueous potassium hydroxide solution and in a condenser. The yield of perfluoro-2-pentyne was calculated from the weight of both and gas chromatographic analysis results. As a result, it was 2.8 mol%. The reaction was carried out at normal pressure, and the gas space velocity “GHSV” was 875 / hr.

(Comparative Example 2)
<1,1,1,2,4,4,5,5,5-nonafluoro-2-pentene and 1,1,1,3,4,4,5,5,5 using cesium fluoride supported catalyst -Reaction of a mixture of nonafluoro-2-pentene (350 ° C)>
7.7 g of a cesium fluoride-supported catalyst (20 wt%) in which 20 wt% of cesium fluoride (manufactured by Wako Pure Chemical Industries, Ltd.) is supported on activated carbon is placed in a Hastelloy reaction tube (diameter 12.7 mm, length 200 mm). Filled. The reaction tube was set in an electric furnace and heated to 350 ° C. A mixture of 1,1,1,2,4,4,5,5,5-nonafluoro-2-pentene and 1,1,1,3,4,4,5,5,5-nonafluoro-2-pentene It was fed into the vaporizer at a rate of 0.3 g / min for vaporization, and fed from the bottom of the reaction tube at a constant rate for 1 hour.
The gaseous mixture coming out of the reaction tube was fed in the order of aqueous potassium hydroxide and potassium fluoride pellets to neutralize the generated hydrogen fluoride, and then collected in a condenser cooled with dry ice-ethanol. The product was collected in an aqueous potassium hydroxide solution and in a condenser. When the yield of perfluoro-2-pentyne was calculated from the weight of both and gas chromatography analysis results, it was 3.1 mol%. The reaction was carried out at normal pressure, and the gas space velocity “GHSV” was 320 / hr.

(Comparative Example 3)
<Reaction of 1,1,1,2,3,4,4,5,5,5-decafluoropentane using zeolite (250 ° C.)>
100 g of zeolite (Molecular Sieves 5A, Union Showa Co., Ltd., about 4 mm) was charged into a Hastelloy reaction tube (diameter 25.4 mm, length 300 mm). The reaction tube was set in an electric furnace and heated to 250 ° C. 1,1,1,2,3,4,4,5,5,5-decafluoropentane (manufactured by Mitsui Dupont Fluorochemical) was supplied into the vaporizer at a rate of 0.036 g / min to vaporize the reaction tube. Feeding from the bottom at a constant speed for 1 hour.
The gaseous mixture coming out of the reaction tube was fed in the order of aqueous potassium hydroxide and potassium fluoride pellets to neutralize the generated hydrogen fluoride, and then collected in a condenser cooled with dry ice-ethanol. The product was collected in an aqueous potassium hydroxide solution and in a condenser. When the yield of perfluoro-2-pentyne was calculated from the weight of both and gas chromatography analysis results, it was 20 mol%. The reaction was carried out at normal pressure, and the gas space velocity “GHSV” was 30 / hr.

From the results of the examples, it can be seen that the perfluoroalkyne compound is produced with high yield and efficiency according to the production method of the present invention. When the temperature falls below the range specified in the present invention, the yield decreases (Comparative Example 1 and Comparative Example 2). Further, when a conventional catalyst (zeolite, Comparative Example 3) is used, the efficiency (gas space velocity) is lowered.

Claims (3)

Reacting a dihydrohalogenoalkane compound represented by the following formula (formula 1) and / or a monohydrohalogenoalkene compound (formula 2) in the presence of a metal fluoride at a reaction temperature of 500 ° C. or higher in a gas-phase flow system. A method for producing a characteristic perfluoroalkyne compound.
R ¹ —CHA—CHB—R ² (Formula 1)
R ¹ —CH═CX—R ² (Formula 2)
(In Formulas 1 and 2, R ¹ and R ² are each independently a perfluoroalkyl group having 1 to 6 carbon atoms, and R ¹ and R ² may combine to form a ring. In formula 1, A and B are each independently one halogen atom selected from the group consisting of F, Cl, Br and I. In formula 2, X is from the group consisting of F, Cl, Br and I. One kind of halogen atom selected.) ^{2. The} method for producing a perfluoroalkyne compound according to claim 1, wherein the metal fluoride is supported on a carrier having a specific surface area measured by a BET method of 100 m ² / g or more. R ¹ is perfluoromethyl group, and R ² is a perfluoroethyl group, perfluoro alkyne compound, The method according to claim 1 or 2 perfluoro alkyne compound according perfluoro-2-pentyne.