WO1998040335A1

WO1998040335A1 - Process for producing 1,1,1,3,3-pentafluoropropane

Info

Publication number: WO1998040335A1
Application number: PCT/JP1998/000932
Authority: WO
Inventors: Tatsuo Nakada; Akinori Yamamoto; Noriaki Shibata; Takashi Shibanuma
Original assignee: Daikin Industries, Ltd.
Priority date: 1997-03-12
Filing date: 1998-03-05
Publication date: 1998-09-17
Also published as: JPH10309464A

Abstract

A tetrahalogenopropane as a starting material is chlorofluorinated by reacting it preferably with chlorine and hydrofluoric acid in the presence of a catalyst to thereby obtain 1,1,1,3,3-pentafluoropropane. Thus, 1,1,1,3,3-pentafluoropropane is easily produced from a material which is available or can be synthesized inexpensively.

Description

Specification

1,1,1,3,3-—Methods for producing pennofluorpropane Industrial applications

The present invention is a useful compound that can be used as a refrigerant, a blowing agent, and a cleaning agent as a substitute for CFC (fluorocarbon fluorcarbon) and HCFC (hydrochlorofluorocarbon) used as a cleaning agent. It relates to a method for producing 1,3,3-pentafluoropropane (HFC-245ia). Conventional technology

As a method for synthesizing 1,1,1,3,3-pentafluoropropane, hydrogen fluoride (HF) in the presence of a fluorination catalyst for 1,1,1,3,3-pentachloropropane has been described. Is known.

However, in this method, the reaction is generally performed using pentavalent antimony as a catalyst, but in order to keep the selectivity high and to increase the productivity, the reaction is performed in an HF solvent (that is, in the liquid phase). It is necessary to perform the reaction, and the material of the reactor that can be used under these reaction conditions is limited, and generally expensive materials are required. In addition, a synthesis method by reduction of 1,1,1,3,3-pentachloro-1,2,3-dichloropropane obtained by fluorination of hexaclopropene is also known, but this method involves synthesis of raw materials, And two-step reaction of reduction are required, and the process is complicated.

Furthermore, a method of synthesizing 1,1,1,3,3-pentafluoropropane by hydrogenation of 1,1,1,3,3-pentafluoropropene is also known, but in this method, However, it is difficult to obtain 1,1,1,3,3-pentafluoropropene, which is a raw material, and it is difficult to implement it industrially. Purpose of the invention

An object of the present invention is to easily and economically produce 1,1,1,3,3-pentafluoropropane (HFC-245fa) from raw materials that can be obtained or synthesized at low cost.

Structure of the invention

The present inventors have conducted intensive studies on an efficient and efficient production process of 1,1,1,3,3-pentafluoropropane in order to solve the above-mentioned problems. The inventors have found that the desired product can be easily (in one step) derived by chlorinating propane with chlorine and hydrogen fluoride (HF) in the presence of a specific catalyst, and have completed the present invention. It is.

That is, the present invention provides 1,1,1,3,3-pentafluoropropane by reacting tetrahalogenopropane as a raw material and reacting it with chlorine and hydrofluoric acid in the presence of a catalyst, in particular, It relates to a method for producing 1,1,1,3,3-pentafluoromouth propane (HFC-245fa).

In the production method of the present invention, it is preferable that 1,1,3,3-tetrahalogenopropane, 1,1,1,3-tetraha-α-genopropane or the like be used as a raw material of tetrahalogenopropane.

In the case of 1,1,3,3-tetrahalogenopropane (for example, 1,1,3,3-tetrachloropropane), the salt to trihalomethane such as chloroform, dichlorofluoromethane, chlorodifluoromethane, etc. It can be synthesized by adding fujidani vinyl. In the case of 1,1,1,3-tetrahalogenobutane (for example, 1,1,1,3-tetrachloropropane), tetrahalogenomethane such as carbon tetrachloride, trichlorofluoromethane, dichlorodifluoromethane, etc. Can be synthesized by the addition of ethylene to Furthermore, these tetrahalogenopropanes can be converted to propane having a large amount of fluorine by fluorine and then subjected to chlorine fluorination, thereby leading to 1,1,1,1,3,3-pentafluoropropane.

For example, when 1,1,1,3-tetrachloropropane is fluorinated under appropriate conditions, it can be converted to 1,1,1 trifluoro-3-chloropropane, which can be chlorinated. Alternatively, the raw material may be fluorinated to give 1,1,1,3,3-tetrafluoropropane or 1,1,1,1,3-tetrafluoropropane and then chlorinated.

The raw material thus obtained is preferably passed through a gaseous phase together with chlorine and HF to carry out chlorine fluorination.

As the catalyst that can be used here, activated carbon, an activated carbon in which a metal is supported, or a metal oxide is suitably used.

In the above statement, as the metal supported on the activated carbon, one or more metals selected from the group consisting of chromium, iron, zinc, cobalt, nickel, palladium, and copper are selected. It is preferable from the aspect of the rate. These may be supported in the form of hydrochloric or nitrate salts. Before the reaction, heat treatment, fluorination treatment with HF, or the like may be performed. When nitrate is used, it changes to the corresponding oxide by heat treatment.

It is also possible to use a metal oxide alone as a catalyst. Examples of such metal oxides include one or more oxides selected from the group consisting of oxides of chromium, iron, zinc, copper, nickel, aluminum, magnesium, calcium, and barium. However, it is preferable in terms of the selectivity of the target.

In the above chlorine fluorination reaction, if the amount of chlorine to be reacted is small, the chlorination does not proceed, and as a result, the amount of unchlorinated substances increases, and If chlorination progresses too much, compounds will increase.

Such unchlorinated products can be led to the target 1,1,1,3,3-pentafluoropropane by separating from the target product after the reaction and then performing chlorine fluoride filtration again. However, if the amount of chlorine is made too low, it will be costly and inefficient to recover it. Also, overdoing or reducing the yield of unrecoverable, over-chlorinated products is also inefficient, and is still inefficient.

Therefore, it is desirable that chlorine be introduced in an amount of about 0.3 to 1.2 times the molar amount of the introduced raw material.

Although the theoretically necessary amount of HF is 1 to 5 times the molar amount of the raw material to be introduced, it is preferable to use about 0.5 to 5 times the HF with respect to this necessary amount.

In this case, it is not necessary to carry out the reaction at less than the stoichiometric amount in order to increase the conversion rate and to suppress the deterioration of the catalyst. When used, the reaction may be performed in a substoichiometric amount. The upper limit is also not particularly limited, but from the viewpoint of the efficiency of the reactor, the reaction is not carried out with HF being at least 5 times the theoretical amount. More preferably, 1 to 3 times the amount of HF is used.

Further, in the production method of the present invention, in order to increase the selectivity of the target substance, the product is further fluorinated to obtain 1,1,1,3,3-pentanofluoropropane following the chlorine fluorination described above. It can also be manufactured.

Specific examples of this product include 1,1,1-trifluoro-3-co-opening α-2-propene, 1,1-difluoro-1,3-dicloα-2-propene, and 1-fluoro-1,4-propene. Olefins such as 1,3-trichloro-2-propene and 1,1-difluoro-3,3-dichloro-2-propene are exemplified. You. By fluorinating these, 1,1,1,3,3-pentafluoropropane can be produced.

In addition, non-halogenated products, such as 1,1,1,1-trifluoro-2-propene and 1,1, difluoro-3-chloro-2-propene, which are co-produced, are again It may be recycled by subjecting it to the above chlorine fluorination step.

In addition, the by-products of fluorination, and the raw materials 1,1,1-trifluoro-3-chloro-1,2-propene, 1,1,1,3-trifluoro-2-propene, etc., are recovered again. It is recycled by subjecting it to a fluorination reaction.

The fluorination can be performed by reacting with HF in the presence of a catalyst. ', One or two selected from the group consisting of antimony halide, niobium genide and tantalum halide The above-mentioned halides can be mentioned, or the fluorination reaction can be carried out in the gas phase by using a chromium, aluminum, iron or nickel nitride or halide as a catalyst. Industrial applicability

According to the production method of the present invention, 1,1,1,3,3-pentafluoropropane is obtained by using tetraha π-genopropane as a raw material and reacting it with chlorine and hydrofluoric acid in the presence of a catalyst. Thus, the desired product can be easily derived by subjecting easily obtainable or synthesizable tetrahalogenopropane to chlorine fluorination with chlorine and fluorine (HF) in the presence of a specific catalyst.

Example

Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to the following examples. Example 1

745 g (6.2 mol) of black-mouthed form was placed in a 1 L autoclave, and 9.9 g (0.1 ml 1) of copper chloride and 65 g (0.5 ml 01) of dibutylamine were placed therein.

After cooling, the inside of the autoclave was replaced with nitrogen, and then the pressure was reduced. 90 g (3 mol 1) of vinyl chloride were introduced, and the temperature was returned to room temperature. Thereafter, the reaction temperature was increased to 120 over 1 hr, and the reaction was carried out for 5 hours. After the reaction, the reaction solution was washed with 1N hydrochloric acid and subjected to GLC (gas-liquid chromatography: the same applies hereinafter) analysis. The analysis results were as follows.

result of analysis:

PVC 12.9%

Black mouth Holm 64.6%

1,1,3,3-tetrac α-mouth propane 20.2%

Other 1.6%

Thus, it is clear that 1,1,3,3-tetrachloropropane can be obtained from Shiridani vinyl and black mouth form with a conversion of 63% and a selectivity of 93%.

5 ο

After that, rectification was performed to obtain 144 1,1,3,3-tetraclopropane.

Next, a reaction tube having a diameter of 20 mm was filled with 25 g of activated carbon supporting iron chloride, and the temperature was adjusted to 300C. 20 cc of chlorine and 200 cc of HF were introduced into the reaction tube, and the 1,1,3,3-tetrachlorobutane synthesized as described above was vaporized and introduced at 20 cc.

The reaction gas was washed with an aqueous solution of a hydroxylic lime and a sulfuric acid lime, then dried by passing through a chloridized calcium tower, and subjected to GLC analysis. The analysis results are as follows Atsuta.

result of analysis:

, 1, 3, 3—Penu Fluoropropane 3, 5%

, 1,3—tetrafluo mouth—2-propene 1.5%

, 1-trifluoro-3-chloro-2-propene 26.8% Difluro π-3-chloro-1-propene 29.7%

—Difluoro-1,3-dichloro-2-propene 10.7% Difluoro-1,3,3-dic sigma-low 2-propene 12.5% Other 15.3% As shown in the results above, one step by chlorine fluorination Thus, 1,1,1,3,3-pentafluoropropane can be obtained.

Example 2

615 g (4. Omo 1) of carbon tetrachloride was placed in a 1 L autoclave, and 6.7 g of copper chloride and 25.9 g (0.2 mol) of dibutylamine were placed therein.

After cooling, the inside of the autoclave was replaced with nitrogen, and then the pressure was reduced. 36 g (l. 4mo1) of ethylene was introduced, and the temperature was returned to room temperature. Thereafter, the reaction temperature was increased to 120 over 2 hours, and the reaction was carried out for 6 hours. After the reaction, the resultant was washed with 3 N hydrochloric acid, and subjected to GLC analysis. The analysis results are as follows.

result of analysis:

Carbon tetrachloride 85.6%

1,1,1,3-tetraclopropane 13.9%

Other 0.5%

Thus, from carbon tetrachloride and ethylene, the conversion was 14% and the selectivity was 97. %, It was found that 1,1,1,3-tetraclopropane was obtained. After that, rectification was performed to obtain 86.1 £ of 1,1,1,3-tetraclopropane.

Next, a reaction tube having a diameter of 2 Omm was filled with 25 g of activated carbon supporting iron chloride. 20 cc of chlorine and 200 cc of HF were introduced into the reaction tube, and the 1,1,1,3-tetrachlorobutane synthesized as described above was vaporized and introduced at 20 cc.

The reaction gas was washed with an aqueous solution of a hydroxylic lime and a sulfuric acid lime, then dried by passing through a chloridized calcium tower, and subjected to GLC analysis. The analysis results are as follows.

result of analysis:

丄 ί 1 ,, 1, 3, 3-pentafluoropropane 5.% ,, ,, 1, 3-tetrafluoro-2-propene 0.8% 丄, 丄 >> 1-Trifluoro-3- 2-propene 16.1% above, 丄, 1-trifluoro-2-propene 52. Ζ%

-Difluoro-1,3-dichloro-2-propene 2.5% Other 22. As shown above, chlorine fluorination gives 1,1,1,3,3-pentafluoropropane in one step. It became clear that it could be done.

Example 3

The reaction was carried out in the same manner as in Example 1, except that the metal salt supported on the activated carbon was changed to chromium nitrate. The analysis results of the reaction product were as follows, and it was found that the desired product was obtained.

result of analysis:

1,1,1,3,3-pentafluoropropane4.8% 1, 1, 3-tetrafluoro-2-propene 0.9%

1,1-Trifluoro-3-chloro-2-propene 28.% 1-Difluoro-3-chloro-1- 2-pi π pen 18.6%

1-Difluoro-1,3-dichloro-2-propene 18.2% 1-Difluoro π-3,3-Dichloromouth 2-propene 1 1.7% Others 16.1% Example 4

The reaction was carried out in the same manner as in Example 1, except that the metal salt supported on the activated carbon was changed to zinc chloride. The analysis results of the reaction product are as follows, and it was found that the desired product was obtained.

result of analysis:

1,1,3,3-pentafluor α-propane 5.1%

1, 1, 3-—tetrafluo mouth— 2-propene 1.0%

1,1-Trifluoro-3-chloro-2, propene 27.6% 1-Difluoro-3-alk π-1,2-pu π pen 24.8%

1 difluoro-1,3-dichloro-2-propene 1 1.6% 1 difluoro-1,3-dichloromouth 2-propene 13. SH other 15.5% Example 5

The reaction was carried out in the same manner as in Example 1, except that the metal salt supported on the activated carbon was changed to cobalt chloride. The analysis results of the reaction product were as follows, and it was found that the desired product was obtained.

result of analysis:

1,1,1,3,3-pentafluoropropane 4.9%

1, 1, 1, 3-tetrafluoro-2-propene 0.7% 1, 1, 1-Trifluoro-1-chloro-2-propene 26.7%

1,1 difluoro α- 3 -chloro-one 2-propene 22.1% 1,1 difluoro π- 1,3-dichloro-one 2-propene 15.8%, 1,1-difluoro-3,3-dichloro-2 —Propene 12.2% Other 17.6% Example 6

The reaction was carried out in the same manner as in Example 1, except that the metal salt supported on the activated carbon was changed to nickel chloride. The analysis results of the reaction product were as follows, and it was found that the desired product was obtained.

result of analysis:

1,1,3,3-pentafluoropropane 5.5%

1,1,3-tetrafluoro-2-propene 1.1% 1, 1-trifluoro-3-chloro-2-propene 22.6%

1-difluoro-3-chloro-2-propene 28.4% 1 difluoro-1,3-dic π-law 2-propene 13.2% 1 difluoro-3,3-dichloro-2-propene 1 0.6% other 18.6 % Example 7

The reaction was carried out in the same manner as in Example 1, except that the metal salt supported on the activated carbon was changed to copper nitrate. The analysis results of the reaction product are as follows, and it was found that the desired product was obtained.

result of analysis:

1, 1, 1, 3, 3-pentafluoropropane 6.9%

1, 1, 1, 3-tetrafluoro-2-propene 1.2% 1, 1, 1-trifluoro α-3-kuguchi-ichi 2-propene 19.8% 1,1-difluoro-1—black mouth 2-propene 22.5%

1,1-Difluoro-1,3-dichloro-1-propene 14.8% 1,1-Difluoro-3,3-dichloro-1-propene 14.1% Others 20.1% Example 8

The reaction was carried out in the same manner as in Example 1, except that the catalyst was changed to chromium oxide. The analysis results of the reaction product are as follows, and it was found that the desired product was obtained.o

result of analysis

, 1, 3, 3—Penu Fluoropropane 3 1%

, 1,3-tetrafluoro-2-propene 0 2%

, 1-Trifluoro-3-chloro-2-propene 1 5 5%

-Difluoro-1-chloro-2-propene 25 2%

—Difluoro-1,3-dichloro-1-propene 28 S% Difluoro-3,3-dichloro-2-propene 1 2 Others 13.3% Example 9

The reaction was carried out in the same manner as in Example 1, except that the catalyst was changed to iron oxide. The analysis results of the reaction product were as follows, and it was found that the desired product was obtained.

result of analysis

1,1,1,3,3-pentafluoropropane 5. S% 1,1,1,3-tetrafluoro-2-propene 0.9% 1,1,1-trifluoro-3-chloro 2-propene 1 9.9% 1, 1-difluoro 3-chloro-2-phenyl π pen 22.7% 1,1 difluoro-1,3-dichloro-2-propene 20,0% 1,1 difluoro-3,3-dichloro-2-propene 1 5.796 Other 15.0% Example 10

1,1,3,3-tetrachloropropane obtained in the same manner as in Example 1 was fluorinated in HF using SbF ₅ as a catalyst to obtain 1,1,3,3-tetrafluoropropane.

A reaction tube having a diameter of 2 Omm was filled with 25 g of activated carbon supporting iron chloride, and the content was adjusted to 300. While introducing 20 cc of chlorine and 200 cc of HF, 1,1,3,3-tetrafluoropropane synthesized as described above was vaporized and introduced at 20 cc.

result of analysis

1 3,3-Pentafluorop π-pan 1 1.6% 13-Tetrafluoro-2-propene 17.9% 3 Trifluoro-2-propene 28.6% 3 3-Tetrafluor mouth 2-propene 22.7% 3 -Trifluoro-1-monochloro-2-propene 10.7% 3-trifluoro-3 -Chloro mouth 2-propene 6.2% Others 2.3% or more It is clear that 1,1,1,3,3-pentafluoropropane can be obtained, Example 1 1

1,1,1-Trifluoropropane is brominated to form 1,1,1-Trifluoro 3-propidoprono. I got it.

A reaction tube having a diameter of 2 Omm was filled with 25 g of activated carbon supporting iron chloride, and this was made 300. In addition to introducing 20 cc of chlorine and 200 cc of HF, 1,1,1''fluoro-bromo-3-bromopropane synthesized as described above was vaporized and introduced into 20 cc.

The reaction gas was washed with an aqueous solution of a hydroxylic lime and a sulfuric acid lime, then dried by passing through a chloridized calcium tower, and subjected to GLC analysis. The analysis results are as follows 7 ₀

result of analysis

1,2,3,3-Pentafluoropropane 72%, 1,3-Tetrafluoro-2-propene 13%, 1-Trifluoro-3-chloro-1-2-piπ pen 20 5%, 1-1 Trifluoro-2-propene 56 5% Difluoro-1,3-dic α-one 2-propene 1 9% Others 1 2.6% As shown above, chlorine fluorination enables 1,1,1,1, 3, 3-pentafluor ο It has become clear that propane can be obtained.

Example 1 2

1,1,3,3-Tetrachlorobroja was prepared in the same manner as described in Example 1. I got it.

A reaction tube having a diameter of 20 mm was filled with 25 g of activated carbon supporting iron chloride, and the temperature was raised to 300 ° C. 20 cc of chlorine and 200 cc of HF were introduced, and the 1,1,3,3-tetrachloropropane synthesized as described above was vaporized. Introduced 20 cc.

result of analysis

1,3,3-pentafluoropropane 3.5%, 1,3-tetrafluoro-2-propene 1.5%, 1-trifluoro-3-chloro-2-propene 26.8% difluoro-3-chloro Mouth 2—Propene 29.7% —Difluoro-1,3-Diclo Mouth 2—Propene 10.7% Difluoro-3,3-dichloro-1-2-propene 12.5% Others 15.3% or more In addition, it was revealed that tetrahalogenopropene can be obtained from tetrachloropropane by chlorine fluorination. The thus obtained tetrahalogenopropene was subjected to liquid phase fluorination by the following method. 50 g of 1,1,1-trifluoro-3-chloro-2-monopropene, 5 g of antimony pentafluoride and 100 g of HF obtained as above are placed in a 200 ml autoclave, and the mixture is treated at 80 ° C for 3 hr. Reacted. Reaction pressure is 10 kg

/ cm ² and the generated HC 1 was removed.

After the reaction, generated HC1, excess HF and generated organic matter were extracted from the reactor through a washing tower. After washing with water, the product was passed through a calcium chloride tower, and the product was trapped with a dry ice-acetone trap. G L

The analysis by C was as follows.

result of analysis:

CF ₃ CH ₂ CHF ₂ 98.2% P / JP

CF ₈ CH = CHF 0.7%

CF ₃ CH ₂ CHFC 1 0.%

CF ₃ CH = CC 1 H 0.3%

Thus, it became clear that 1,1,1,3,3-pentafluoropropane can be obtained almost quantitatively and efficiently. The by-produced tetrafluoropopene was able to be derived into the desired pen-fluorinated π-propane by recycling to the above liquid phase fluorination step. By this recycling, the selectivity of the target pentafluoropropane was improved to 99.3%.

Example 13

In Example 12, gas-phase fluorination was performed instead of liquid-phase fluorination. A reaction tube having a diameter of 20 mm was filled with 25 g of Futsudani chrome, and this was set to 300. Introduce 200 cc of HF and vaporize the 1,1,1,1-trifluoro-3-chloro-2-propene synthesized as described above to introduce 20 cc and introduce 7 cc.

The reaction gas was washed with aqueous hydroxide and aqueous sodium sulfite, then dried by passing through a chloride tower, and subjected to GLC analysis. The analysis results are as follows:

F 3 H 2 C n F 2 67 2%

CF ₃ CH = CHF 8 5%

CF ₃ CH = CC 1 H 24

Thus, it has become clear that 1,1,1,3,3-pentafluoropropane can be obtained efficiently. The by-produced tetrafluoropropane could be derived to the desired pentafluoropropane by recycling to the above-mentioned self-phase fluoridation process. Through this recycling, the desired pentafu Lulopropane selectivity increased to 95%.

Example 14

In Example 12, 1,1-difluoro-3-chloro-2-propene produced as a by-product was recycled to the above-mentioned chlorine fluorination step. According to GLC analysis results, the selectivity of 1,3,3-Penyu fluo-α-pan was 86%.

Claims

The scope of the claims

1. Production of 1,1,1,3,3-pentafluoropropane using tetrahalogenopropane as raw material to obtain 1,1,1,3,3-pentafluoropropane through a chlorine fluorination process Method.

2. The method for producing 1,1,1,3,3-pentafluoroα-propane according to claim 1, wherein the chlorine fluorination is carried out by reacting the tetrahacogenop π-pan with chlorine and hydrofluoric acid.

3. The 1,1,1,3,3-pentafluorolob π according to claim 1 or 2, wherein 1,1,3,3-tetrahalogenopropane is used as the tetrahalogenopropane. Bread manufacturing method.

4. 1,3,3-tetrahalogenob α pan

The method for producing 1,1,3,3-pentafluoropropane described in claim 3 using 1,3,3-tetrachloropropane.

5. The 1,1,1,3,3-pentafluorolob π according to claim 1 or 2, wherein 1,1,1,3-tetrahydrohalogeno π pan is used as the tetrahalogenopropane. Bread manufacturing method.

6. 1,1,3-tetrahalogenopropane

The method for producing 1,1,3,3-pentafluoropropane according to claim 5, wherein 1,1,3-tetraclopropane is used.

7. The method according to any one of claims 1 to 6, wherein the chlorine fluorination is performed after fluorinating all or a part of the hagen atoms in the raw material. , 1,3,3-Penyu Fluoropropane production method.

8. After fluorinating the raw material to 1,1,3,3-tetrafluoropropane or 1,1,1,3-tetrafluoropropane, The method for producing 1,1,1,3,3-pentafluoropropane according to claim 7, wherein the chlorine fluorination is performed.

9. Activated carbon or a catalyst supporting a metal on activated carbon is used as a catalyst for the chlorine fluorination reaction, wherein 1, 1, 1, 1 described in any one of claims 1 to 8 of the claims. For the production of, 3,3-pentafluoropropane.

10. Metals supported on activated carbon include chromium, iron, copper, cobalt, nickel, and nickel. 10. The method for producing 1,1,1,3,3-pentafluoropropane according to claim 9, wherein one or more metals selected from the group consisting of radium and copper are used.

11. The metal oxidized product is used as a catalyst for the chlorine fluorination reaction, wherein the metal sulfide is used as a catalyst for the chlorine fluorination reaction. Method for producing Penyu Fluoropropane.

1 2. As the metal oxide, one or two or more oxides selected from the group consisting of chromium, iron, zinc, cono-kort, nigel, aluminum, magnesium, calcium and barium oxides A method for producing 1,1,1,3,3-pentanofluoropropane as described in claim 11 used.

1 3. The 1,1,3,3-tetrahalogenopropane is synthesized by the addition of vinyl chloride to methane trichloride, wherein the 1,1,1,3,3- How to use pentafluoropropane.

1 4. Using chloroform as the trihalomethane, 1, 1,

The method for producing 1,1,3,3-pentafluoropropane according to claim 13, wherein 3,3-tetraclopropane is synthesized.

1 5. 1,1, 1,3-tetrahalogenopropane It is synthesized by addition of ethylene to halogenomethane, wherein 1,1,1,3,3-pentanofluoropropane! ¾i way.

1 6. Using carbon tetrachloride as the tetrahalogenomethane,

The method for producing 1,1,1,3,3-pentafluoropropane according to claim 15, wherein 1,1,3-tetraclopropane is synthesized.

1 7. The 1,1,1,2,3,4,5,6,7,8,7,8 compound according to any one of claims 1 to 16, wherein the tetrahalogenopropane is chlorinated and the product is further fluorinated. Method for producing 3,3-pentafluoropropane.

1 8. The first of the claims, wherein the product is a refining compound

The method for producing 1,1,1,3,3-pentyl full-propene lopropane described in paragraph 7.

1 9. The process for producing 1,1,1,3,3-pentafluoropropane described in Item 17 of the claim, wherein the fluorination is carried out by reacting with HF in the presence of a catalyst. .

20. The reaction in the HF using one or more halides selected from the group consisting of antimony halides, diobogen halides and tantalum halides as the medium. Item 19. The method for producing 1,1,1,3,3-pentafluoropropane described in Item 19.

2 1. Chromium, aluminum, or nickel oxide or halide is used as the previous catalyst, and reacts with the HF in the gas phase. 1,1,3,3-Pentafluorob A method for producing bread.