JPH02204443A - Production of hydrogen-containing pentafluoropropanes and hydrogen-containing tetrafluoropropanes - Google Patents

Abstract

PURPOSE:To produce the title compound useful as a blowing agent, refrigerant, detergent, etc., in high selectivity, in high purity and in high yield by reducing a difluoromethylene group-containing pentafluoropropane with hydrogen in the presence of a hydrogenating catalyst. CONSTITUTION:A difluoromethylene group-containing pentafluoropropane shown by formula I (n is 0<=-<=2) is reacted with hydrogen in the presence of a hydrogenating catalyst to give a hydrogen-containing pentafluoropropane shown by formula II (n is 1<=-<=3) and a hydrogen-containing tetrafluoropropane shown by formula III (n is 1<=-<=4). For example, 1,1,3-trichloro-1,2,2,3,3- pentafluoropropane, 1,1,1-trichloro-2,2,3,3,3-pentafluoropropane or 1,1- dichloro-2,2,3,3,3-pentafluoropropane is preferable as the difluoromethylene group- containing pentafluoropropane as the starting raw material.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention relates to hydrogen-containing pentafluoropropanes having a difluoromethylene group (C3H, C13-nFa; 1≦n
≦3) and hydrogen-containing tetrafluoropropanes (C3H
nC14-nFa: 1≦n≦4). Hydrogen-containing pentafluoropropanes and hydrogen-containing tetrafluoropropanes having a difluoromethylene group are expected to be used as blowing agents, refrigerants, cleaning agents, etc., similar to conventionally used fluorocarbons.

[Prior art and problems to be solved by the invention] Conventionally, as a synthesis route 1 for hydrogen-containing pentafluoropropanes having a difluoromethylene group, 1-chloro-1,2,2-trifluoropropanes were synthesized in the presence of aluminum chloride. A synthesis method is known in which chlorodifluoromethane or the like is added to ethylene having a difluoromethitone unit such as fluoroethylene. However, this method has the disadvantage that it requires multiple purification steps to obtain a highly pure product because it simultaneously produces the desired product and a reaction by-product that has a methylene group other than difluoromethylene that has a boiling point close to that of the desired product. have.

[Means for Solving the Problems] The present inventor has developed hydrogen-containing pentafluoropropanes having a difluoromethylene group (C3HnCl3-F5;1
≦n≦3) and hydrogen-containing tetrafluoropropanes (C
3H, CIJ-, , FJ: i≦n≦4), as a result of intensive studies, we found that pentafluoropropanes having a difluoromethylene group (C3H-C
I3~. F et al.: They discovered that hydrogen-containing pentafluoropropanes can be obtained in high yield by reducing 0≦m≦2) with hydrogen in the presence of a hydrogenation catalyst, and have come to provide the present invention. be.

The details of the present invention will be explained below along with examples.

That is, it was discovered that when pentafluoropropanes having a difluoromethylene group are subjected to catalytic hydrogen reduction, hydrogen-containing pentafluoropropanes and hydrogen-containing tetrafluoropropanes having a difluoromethylene group are produced in good yield as shown in the formula below. .

CaH, Ch-, Fs C3HnC13
−nFSO≦m≦2 1≦n≦
・3C3HI, Cla-l, F a 1≦n≦4 In this reaction, group ■ elements, rhenium, zirconium,
Various hydrogenation catalysts formed from tungsten, etc., or combinations thereof, can be used.

Pentafluoropropanes having a difluoromethylene group (C3H-Ct3-F5: 0≦m≦2) used as raw materials
) is 1,,3-trichloro-1,2,2,3,
3-pentafluoropropane (R-215ea), 1,
1゜1-■・Rechloro2.2.3.3.3-pentafluoropropane (R-215eb), 1,1-dichloro-2,2,3,3,3-pentafluoropropane (R
-225ea), 1°3-dichloro-1,1,2,2,
3-pentafluoropropane (R-225eb), 1
-dichloro-1,2,2,3,3-pentafluoropropane (R-225cc), 1-chloro-1,2,2,3
,3-pentafluoropropane<R-235e a )
, 1-chloro-2,2,3,3,3-pentafluoropropane (R-235cb), 1-chloro-1,1,2
, 2°3-pentafluoropropane (R235cc), all of which are known.

In the present invention, examples of the hydrogenation catalyst carrier include:
Alumina, activated carbon, etc. are suitable. As the supporting method, a conventional noble metal catalyst preparation method can be applied. In addition, in order to obtain stable characteristics, it is preferable to subject the catalyst to a reduction treatment in advance before use, but this is not always necessary.

Compounds of such metals are at least partially reduced.

The proportions of hydrogen and feedstock can be varied widely. Typically, a stoichiometric amount of hydrogen is used to remove the halogen atom, but pentafluoropropanes with a difluoromethylene group (
C3HIIC13-11F5; O≦s≦2) Using a considerably larger than stoichiometric amount of hydrogen, e.g. Good too.

In the gas phase reaction, the reaction temperature is suitably 100 to 450°C, particularly preferably 100 to 300'C, and the contact time is usually 0.1 to 300 seconds, particularly preferably 2 to 60 seconds.

When carrying out the reaction in a liquid phase, alcohols such as ethanol and isopropyl alcohol,
Examples include acetic acid and pyridine, but it is also possible to carry out without solvent. The reaction temperature in liquid phase reaction is room temperature to 150℃
is preferable, and the reaction pressure is preferably normal pressure to 10 kg/aJ.

Hydrogen-containing pentafluoropropanes (C3H0CL3-nFs) having a difluoromethylene group produced by the reaction
;1≦n≦3), 1,1-dichloro-2,
2,3,3,3-pentafluoropropane (R-225
ca), 1,3-dichloro-1,1,2,2,3-pentafluoropropane (R-225cb), , 1-dichloro-1°2, 2.3.3-pentafluoropropane (
R-225cc), ■-ri4ro, 2.2.3.3-pentafluoropropane (R-235ca), 1-chloro-2,2,3,3,3-pentafluoropropane (R-
235cb), 1-chloro-1,1,2,2,3-pentafluoropropane (R-235, cc), 2.2
．． 3-pentafluoropropane (R-245ca),
,,2,2-pentafluoropropane (R-245cb
), but also hydrogen-containing tetrafluoropropanes (C3Hn
Cla −, F a ; 1≦n≦4), 1
-chloro-1,1,2,2-tetrafluoropropane (
Examples include R-244cc), L, and 2,2-tetrafluoropropane (R-254cb), which can be separated by ordinary operations such as distillation.

[Example] Examples of the present invention are shown below.

Preparation Example 1 Coconut shell charcoal was immersed in a solution prepared by adding 1% by weight of hydrochloric acid to pure water to impregnate the inside of the pores with the solution. Add palladium chloride and nickel chloride to this in a metal component weight ratio of 8:
The total weight of metal components is 0 for the weight of activated carbon at a ratio of 2
．． An aqueous solution containing only 5% of the solution was dropped little by little to cause the ionic components to be adsorbed onto the activated carbon. Add a hydrazine aqueous solution to this and reduce it rapidly. After washing with pure water,
It was dried at 50°C for 5 hours.

Preparation Example 2 Crushed coconut shell charcoal was immersed in pure water to impregnate the inside of the pores with water. To this, an aqueous solution containing palladium chloride and potassium tungstate dissolved at a weight ratio of metal components of 9:1 and only 0.5% of the total weight of metal components relative to the weight of activated carbon was added little by little to adsorb the ionic components to the activated carbon. I let it happen. After washing with pure water, it was dried at 150° C. for 5 hours. Next, after drying in nitrogen at 550°C for 4 hours, hydrogen was introduced and the mixture was maintained at 300°C for 5 hours for reduction.

Example 1 Palladium catalyst supported on activated carbon (supported amount 2 0.5% by weight)
Inner diameter 2.54cm, length 100cm filled with 400cc
A reaction tube made of Inconel 600 of 1.5 m was immersed in a salt bath furnace.

Hydrogen and starting materials, 1-trichloro-2,2,3,3
, 3-pentafluoropropane is gasified at a molar ratio of 1=1 and introduced into the reaction tube.The reaction temperature is 200'C1.
The contact time was 20 seconds. After removing the acid content, the reaction product was collected in a trap cooled to -78°C.

The collected reaction products were subjected to gas chromatography and N
It was analyzed using MR and the results are shown in Table 1.

Examples 2 to 3 , 1-trichloro-2°2, 3.
3. A hydrogenation reaction of 3-pentafluoropropane was carried out and the reaction product was analyzed. The results are shown in Table 1.

Table 1 Example 4=6 Same as Example 1 except that the catalyst shown in Table 2 prepared in the same manner as Preparation Example 2 was used except that the catalyst components were those in Table 2, and the reaction conditions shown in Table 2 were used. Then, i,,t,i
-Trichloro-2,2,3,3,3-pentafluoropropane was hydrogenated and the reaction product was analyzed. The results are shown in Table 2.

Table 2 Examples 7 to 8 The reaction conditions shown in Table 3 were used, using a hornworm medium prepared in the same manner as in Preparation Example 2, except that the catalyst components were adjusted to the weight ratios shown in Table 3 and the reduction temperature was set to 300°C. 1-Trichloro-2,2,3゜3.3-
The hydrogenation reaction of pentafluoropronone was carried out at 1 tb and the reaction product was analyzed. The results are shown in Table 3.

Examples 9-10 A catalyst prepared in the same manner as in Preparation Example 2 was used, except that the weight ratio of the catalyst components was as shown in Table 4, and the reduction temperature was 300°C. The reaction conditions shown in Table 4 were used.↓False/False 31 In the same manner as in Example 1, a hydrogenation reaction of 1-trichloro-2.2.3.3°3-pentafluoropropane was carried out and the reaction product b1 was analyzed. The results are shown in Table 4G.

Table 3 Table 4 Table 5 Examples 11 to 13 The catalyst components are shown in Table 5, and the supported amount is 2.0% by weight.
In the same manner as in Example 1, except that the hydrogenation catalyst shown in Table 5 prepared in the same manner as in Preparation Example 1 was used, and the reaction conditions shown in Table 5 were used, ,,3-dolichloro-1,2 ，
A hydrogenation reaction of 2,3,3-pentafluoropropane was carried out and the reaction product was analyzed.

The results are shown in Table 5.

Examples 14 to 16 The catalyst components are shown in Table 5, and the supported amount is 2.0% by weight.
,,3-trichloro-1,2 was prepared in the same manner as in Example 1 except that the hydrogenation catalyst shown in Table 6 prepared in the same manner as in Preparation Example 2 was used, and the reaction conditions shown in Table 6 were used. ，
A hydrogenation reaction of 2,3,3-pentafluoropropane was carried out and the reaction product was analyzed.

The results are shown in Table 6.

Table 6 Table 7 Examples 7 to 18 The catalyst component composition was set to the weight ratio shown in Table 7, and the reduction temperature was set to 300.
, 3-trichloro-1,2,2,3 in the same manner as in Example 1 except that the catalyst was prepared in the same manner as in Preparation Example 2, and the reaction conditions shown in Table 7 were used. ,3-
A hydrogenation reaction of pentafluoropropane was carried out and the reaction products were analyzed. The results are shown in Table 7.

Examples 19-20 The catalyst component composition was set to the weight ratio shown in Table 8, and the reduction temperature was set to 300°C.
I,,3-trichloro-1°2,2. 3.
3 - A hydrogenation reaction of pentafluoropropane was carried out and the reaction product was analyzed. The results are shown in Table 8.

Table 8 Example 21 1,1-dichloro-2,2,3,3,3 as starting material
The reaction was carried out in the same manner as in Example 1 except that -pentafluoropropane was used and the reaction conditions shown in Table 9 were used, and the reaction products were analyzed. The results are shown in Table 9.

Example 22 As starting material, 3-dichloro-1,1,2,2,3-
The reaction was carried out in the same manner as in Example 1 except that pentafluoropropane was used and the reaction conditions shown in Table 9 were used, and the reaction products were analyzed. The results are shown in Table 9.

Example 23 As starting material, 1-dichloro-1,2,2,3,3-
The reaction was carried out in the same manner as in Example 1 except that pentafluoropropane was used and the reaction conditions shown in Table 9 were used, and the reaction products were analyzed. The results are shown in Table 9.

Example 24 The reaction was carried out in the same manner as in Example 1 except that 1-chloro-2,2,3,3,3-pentafluoropropane was used as the starting material and the reaction conditions shown in Table 10 were used. An analysis was conducted. The results are shown in Table 10.

Example 25 The reaction was carried out in the same manner as in Example 1 except that 1-chloro-1,1,2,2,3-pentafluoropropane was used as the starting material and the reaction conditions shown in Table 10 were used. An analysis was conducted. The results are shown in Table 10.

Example 26 The reaction was carried out in the same manner as in Example 1 except that 1-chloro-1,2,2,3,3-pentafluoropropane was used as the starting material and the reaction conditions shown in Table 10 were used. An analysis was conducted. The results are shown in Table 10.

Table 9 Table 10 Example 27 Prepared in the same manner as in Preparation Example 1 except that the catalyst component was platinum and the supported amount was 1% by weight; a hydrogenation catalyst was also used, and the starting materials were The reaction was carried out in the same manner as in Example 1 except that 2,3,3,3-pentafluoropropane was used and the reaction conditions shown in Table 11 were used, and the reaction products were analyzed. The results are shown in Table 11.

Example 28 Using a hydrogenation catalyst prepared in the same manner as in Preparation Example 2 except that the catalyst component was platinum and the supported amount was 1% by weight, the starting material was 3-dichloro-1,1,2,2, The reaction was carried out in the same manner as in Example 1 except that 3-pentafluoropropane was used and the reaction conditions shown in Table 16 were used, and the reaction products were analyzed. The results are shown in Table 11.

Example 29 Using a hydrogenation catalyst prepared in the same manner as in Preparation Example 1 except that the catalyst component was platinum and the supported amount was 1% by weight, the starting material was 1,1-dichloro-1,2,2,3 , 3-pentafluoropropane, and the reaction was carried out in the same manner as in Example 1, except that the reaction conditions shown in Table 11 were used, and the reaction products were analyzed. The results are shown in Table 11.

Table 11 Example 830 Using a hydrogenation catalyst prepared in the same manner as in Preparation Example 1 except that the catalyst components were platinum and j ~ supported amount was 1% by weight, the starting material was 1-chloro-2,2,3,3 , 3-pentafluoropropane, and the reaction was carried out in the same manner as in Example 1, except that the reaction conditions shown in Table 12 were used, and the reaction products were analyzed. The results are shown in Table 12.

Example 31 Using a hydrogenation catalyst prepared in the same manner as in Preparation Example 2 except that the catalyst component was platinum and the supported amount was 2% i%, the starting material was 1-chloro-1,1,2,2,3 The reaction was carried out in the same manner as in Example 1 except that -pentafluoropropane was used and the reaction conditions shown in Table 12 were used, and the reaction products were analyzed. The results are shown in Table 12.

Example 32 Using a hydrogenation catalyst prepared in the same manner as in Preparation Example 1 except that the catalyst component was platinum and the amount of 2 supported was 2% by weight, the starting material was 1-chloro-1,2,2,3, The reaction was carried out in the same manner as in Example 1 except that 3-pentafluoropropane was used and the reaction conditions shown in Table 12 were used, and the reaction product was analyzed. The results are shown in Table 12.

Table 12 Example 33 750 g of 3-trichloro-1,2,2,3,3-pentafluoropropane and a catalyst component of platinum,
7.5 g of platinum catalyst prepared in the same manner as in Preparation Example 2 except that the supported amount was 5% by weight and the carrier was activated carbon powder was charged.
A cooler was attached to the top of the flange of the autoclave, and a valve was attached to the top of the cooler to make it an open system. The temperature of the refrigerant in the cooler was -20°C.

After sufficiently purging the inside of the autoclave with nitrogen, the temperature was raised to 65°C under stirring. Next, hydrogen was blown into the autoclave until the internal pressure reached 2 kg/cm. After that, the internal pressure was always 2 kg.
Hydrogen was introduced at a constant flow rate of /cm2, and the temperature was always around 60°C. The hydrogen flow rate at this time was 560 m12/min. The reaction gas that cannot be condensed in the cooler is passed through water to remove hydrogen chloride, and then passed through a trap cooled with dry ice to collect the condensed gas.

After reacting under stirring for 120 hours in this state, the reaction solution was taken out and the catalyst was separated from the furnace. A mixed liquid of the P liquid and the condensate collected in the trap cooled with dry ice was analyzed by gas chromatography.

The results are shown in Table 13.

[Effect of the invention]

Claims (1)

[Claims] 1. Pentafluoropropanes having a difluoromethylene group (C_3H_mCl_3_-_mF_5; 0≦m
≦2) with hydrogen in the presence of a hydrogenation catalyst. Hydrogen-containing pentafluoropropanes (C_3H
_nCl_3_-_nF_5; 1≦n≦3) and hydrogen-containing tetrafluoropropanes (C_3H_nCl_4_
-_nF_4; 1≦n≦4) manufacturing method. 2. Pentafluoropropanes having a difluoromethylene group are 1,1,3-trichloro-1,2,2,3,3
-Pentafluoropropane.The manufacturing method according to claim 1. 3. Pentafluoropropanes having a difluoromethylene group are 1,1,1-trichloro-2,2,3,3,3
-Pentafluoropropane.The manufacturing method according to claim 1. 4. The production method according to claim 1, wherein the pentafluoropropane having a difluoromethylene group is 1,1-dichloro-2,2,3,3,3-pentafluoropropane. 5. The production method according to claim 1, wherein the pentafluoropropane having a difluoromethylene group is 1,3-dichloro-1,1,2,2,3-pentafluoropropane. 6. The production method according to claim 1, wherein the pentafluoropropane having a difluoromethylene group is 1,1-dichloro-1,2,2,3,3-pentafluoropropane. 7. The production method according to claim 1, wherein the pentafluoropropane having a difluoromethylene group is 1-chloro-1,2,2,3,3-pentafluoropropane. 8. The production method according to claim 1, wherein the pentafluoropropane having a difluoromethylene group is 1-chloro-2,2,3,3,3-pentafluoropropane. 9. The production method according to claim 1, wherein the pentafluoropropane having a difluoromethylene group is 1-chloro-1,1,2,2,3-pentafluoropropane.