JPH05194285A - Production of fluorobutene and fluorobutane - Google Patents

Abstract

PURPOSE:To obtain the subject compound useful as an intermediate for pharmaceuticals and agricultural chemicals and thermal medium, etc., in high yield and selectivity by reacting hexafluorochlorobutene with hydrogen fluoride in the presence of a fluorination catalyst in vapor phase. CONSTITUTION:The objective 1,1,1,2,4,4,4-heptafluorobutene and 1,1,1,2,2,4,4,4- octafluorobutane can be produced by reacting 1,1,1,4,4,4-hexafluoro-2-chloro-2- butene with hydrogen fluoride in the presence of a fluorination catalyst in vapor phase.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a process for producing fluorobutene and fluorobutane, and more specifically to 1,1,
The present invention relates to a method for producing 1,2,4,4,4-heptafluorobutene and / or 1,1,1,2,2,4,4,4-octafluorobutane. 1,1,1,2,4,4,4-heptafluorobutene is not only useful as an industrial chemical or as an intermediate for pharmaceutical and agricultural chemicals, but also hydrogen fluoride (HF)
As a substitute for CFC or HCFC, 1,1,1,2,2,2,4,4,4-octafluorobutane used for foaming or washing or as a heating medium can be obtained by adding the above.

[0002]

2. Description of the Prior Art 1,1,1,2,4,4,4-heptafluorobutene is known to be produced by fluorinating hexachlorobutadiene in the presence of KF.
This reaction is not suitable for industrial use from the viewpoint of the treatment of KCl after the reaction and the cost because KF is used in addition to the complicated operation.

There is no industrially available synthetic method for 1,1,1,2,2,4,4,4-octafluorobutane.

[0004]

SUMMARY OF THE INVENTION The present invention is based on the previously unknown 1,1,1,2,4,4,4-heptafluorobutene and / or 1,1,1,2, Two, four, four,
It is intended to provide an industrial production method of 4-octafluorobutane.

[0005]

The present inventors have found that industrially useful 1,1,1,2,4,4,4-heptafluorobutene and / or 1,1,1,1,2,2, As a result of extensive studies to establish a method for producing 4,4,4-octafluorobutane, 1,1,1,4,4,4-hexafluoro-2, which is easily available, is obtained.
It was found that the desired product was formed by carrying out the gas phase fluorination of chloro-2-butene in the presence of a suitable catalyst. The present invention has been completed.

That is, the present invention relates to reacting 1,1,1,1,4,4,4-hexafluoro-2-chloro-2-butene with hydrogen fluoride in the presence of a fluorination catalyst in the gas phase. Characteristic 1,1,1,2,4,4,4-heptafluorobutene and 1,1,1,2,2,4,4,4-octafluorobutane production method, fluorination catalyst in gas phase 1,1,1,2,4,4,4-heptafluorobutene is reacted with hydrogen fluoride in the presence of 1,1,1,2,
Method for producing 2,4,4,4-octafluorobutane and 1,1,1,4,1,4,4-octafluorobutane in the gas phase in the presence of a fluorination catalyst
1,1,1,1,2,4,4,4-obtained by reacting 4,4-hexafluoro-2-chloro-2-butene with hydrogen fluoride
From a mixture containing heptafluorobutene and 1,1,1,2,2,4,4,4-octafluorobutane, 1,1,1,2,4,
1,1,1,2,2,4,4,4-octafluorobutane characterized by separating 4,4-heptafluorobutene and reacting it with hydrogen fluoride in the presence of a fluorination catalyst A method of manufacturing the same is provided.

The starting material, 1,1,1,4,4,4-hexafluoro-2-chloro-2-butene, can be easily prepared by fluorinating inexpensively available hexachlorobutadiene.

The fluorination catalyst used in the reaction may be a metal fluorinated compound or a metal oxyfluorine compound obtained by fluorinating a metal oxide deposited from a solution of a metal salt using an alkali with HF.

Hydrochloride and nitrate can be used as the metal salt. As the alkali, ammonia, urea or metal hydroxide can be used. As the metal, one kind or a mixture of two or more kinds selected from aluminum, chromium, manganese, nickel and cobalt can be used.

These metal fluorides can be used alone or supported on a suitable carrier. Activated carbon, fluorinated aluminum or the like can be used as the carrier.

The reaction temperature can be appropriately selected from the range of 250 ° C to 450 ° C, but if the reaction temperature is low, the reaction is slow and not practical. If the reaction temperature is raised, the reaction proceeds rapidly and 1,1,1,2,4,4,4-heptafluorobutene is produced, but by raising the reaction temperature, 1,1,1,2,
4,4,4-heptafluorobutene and 1,1,1,2,2,4,
The equilibrium of 4,4-octafluorobutane tilts to the butene side. That is, an appropriate temperature must be selected depending on the ratio of the desired product and the excess amount of HF.

The amount of HF supplied to the reactor is 1, 1, 1,
If it is higher than 4,4,4-hexafluoro-2-chloro-2-butene, the equilibrium tends to the product side and the reaction rate improves. However, if it is increased, the contact time is shortened and the equilibrium cannot be reached. That is, an appropriate amount of HF must be selected depending on the ratio of the desired product and the temperature.

As described above, since these reactions are both equilibrium reactions, the yield can be improved by removing HCl from the reaction system and recycling the product and HF. Further, in order to improve the selectivity of 1,1,1,2,2,4,4,4-octafluorobutane, 1,1,1,2,2,4,4,4 produced from the reaction system is used. -Excluding octafluorobutane, 1,1,1,2,4,4,4-heptafluorobutene may be recycled.

The addition of hydrofluoric acid to 1,1,1,1,2,4,4,4-heptafluorobutene can be carried out in the same reactor in a recycled form, but it is also possible to use a plurality of reactors.

[0015]

Example 1 The metal oxides shown in Table 1 were compressed into tablets having a diameter of 3 mm and a thickness of 3 mm. After 55 cc of this pellet-shaped catalyst was filled in a reaction tube, it was fluorinated with HF. After adjusting the reaction temperature to the temperature shown in Table 1, HF500cc, 1,1,1,4,4,
4-hexafluoro-2-chloro-2-butene (R-1
326) 50 cc of gas was introduced. The product was washed with water and analyzed by GLC. The results are shown in Table 1. In the table, R-
1327 represents 1,1,1,2,4,4,4-heptafluorobutene, and R-338 represents 1,1,1,4,4,4-hexafluorobutane. GLC analysis: PORAPACK-Q 3m Temperature rising from 100 ° C to 10 ° C / min TCD

[0016]

[Table 1]

Example 2 Under the same reaction conditions as in Example 1, the amount of raw material charged was changed and the reaction was carried out. That is, HF500cc, R-132
6,30 cc of gas was introduced. The results are shown in Table 2.

[0018]

[Table 2]

Example 3 Under the same reaction conditions as in Example 1, HF500cc and 1,
The reaction was carried out by introducing 50 cc of 1,1,2,4,4,4-heptafluorobutene in a gaseous state. The results are shown in Table 3.

[0020]

[Table 3]

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Claims (3)

[Claims] 1. A gas phase in the presence of a fluorination catalyst,
1,1,1,4,4,4-hexafluoro-2-chloro-2
1,1,1,2,4,4,4-heptafluorobutene and 1,1,1,2,2,4,4,4-octafluoro, characterized in that butene is reacted with hydrogen fluoride Butane manufacturing method. 2. In the presence of a fluorination catalyst in the gas phase,
1,1,1,2,4,4,4-heptafluorobutene is reacted with hydrogen fluoride 1,1,1,2,2,4,
Method for producing 4,4-octafluorobutane. 3. In the presence of a fluorination catalyst in the gas phase,
1,1,1,4,4,4-hexafluoro-2-chloro-2
-Reacting butene with hydrogen fluoride to give 1,1,1,1,
2,4,4,4-heptafluorobutene and 1,1,1,2,2,
1,4 from a mixture containing 4,4,4-octafluorobutane
Separating 1,1,2,4,4,4-heptafluorobutene,
A method for producing 1,1,1,1,2,2,4,4,4-octafluorobutane, which comprises reacting this with hydrogen fluoride in the presence of a fluorination catalyst.