JPH08239334A - Production of 1,1,1,3,3-pentafluoropropane - Google Patents

Abstract

PURPOSE: To obtain 1,1,1,3,3-pentafluoropropane which is useful as a foaming agent or as a refrigerant for turbo refrigerator by fluorinating 1,1,1,3,3- pentachloropropane in the presence of an antimony catalyst. CONSTITUTION: The liquid-phase fluorination of 1,1,1,3,3-pentachloropropane is carried out using hydrogen fluoride in the presence of an antimony catalyst such as antimony pentachloride at 10-150 deg.C under a pressure of 1-100kg/cm<2> . It is preferred that the catalyst concentration is 0.1-50 mole % based on 1,1,1,3,3- pentachloropropane and the molar ratio of hydrogen fluoride is in the range from 5 to 30. This fluoride compound can be obtained from the corresponding organic chloride through the one-step operation.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is useful as a foaming agent such as polyurethane foam or a refrigerant.
The present invention relates to a method for producing 3,3-pentafluoropropane.

[0002]

2. Description of the Related Art Conventional methods for producing 1,1,1,3,3-pentafluoropropane include CF ₃ -CClX-C.
Method for catalytically hydrogenating F ₂ Cl (Japanese Patent Laid-Open No. 25623/1994)
No. 5), 1,1,3,3,3-pentafluoro-1-
Method of hydrogenating propene with Pd-Al ₂ O ₃ (Izve
st. Akad. Nauk S. S. S. R. , Otd
el. Khim. Nauk. 1960, 1412-1
8; CA 55,349f), a method for hydrogenating 1,2,2-trichloropentafluoropropane (USP2)
942036) and the like are known.

[0003]

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention
Although hydrogen substitution of chlorine atom by hydrogenation described in 56235 or USP 2942036 is a method excellent in reaction rate and selectivity, the deterioration of the catalyst is remarkable,
Further, the raw material fluorinated chlorinated product must be prepared in advance, and there are many difficulties in industrial application. On the other hand, the above-mentioned method of adding hydrogen to an olefin is an excellent method for producing 1,1,1,3,3-pentafluoropropane, but it is 1,1,3,3,3 as a raw material.
It is difficult to obtain -pentafluoro-1-propene, and there is a problem in industrial application.

[0004]

[Means for Solving the Problems] In view of the problems of the prior art, the inventors of the present invention produced 1,1,1,3,3-pentafluoropropane suitable for production on an industrial scale. After intensively investigating various manufacturing processes to establish the method, when the corresponding chlorinated compound is liquid-phase fluorinated with hydrogen fluoride, by using an antimony compound as a catalyst, it is aimed at a high yield. 1,
The inventors have found that 1,1,3,3-pentafluoropropane can be obtained, and arrived at the present invention.

The 1,1,1,3,3-pentachloropropane used in the present invention is a method of reacting vinylidene chloride and chloroform in the presence of a copper amine catalyst (M. Kot).
ora et al., React. Kinet. Catal. Le
tt. , 44, No. 2, 415, 1991), a method of reacting carbon tetrachloride and vinyl chloride in the presence of a copper amine catalyst (M. Kotra et al., J. of Mol. C).
atal. 77, 51, 1992), a method of reacting carbon tetrachloride with vinyl chloride in the presence of a ferrous chloride catalyst (J. of Org. Chem. USSR, 3, 21).
01, 1969) and the like.

That is, the present invention is 1, 1, 1, 3, 3
A liquid phase fluorination of pentachloropropane with hydrogen fluoride to produce 1,1,1,3,3-pentafluoropropane, using an antimony compound as a catalyst.

Antimony catalysts in the liquid phase fluorination of halogenated hydrocarbons with hydrogen fluoride are generally SbF.
It is presumed that the mixed state of aXb (X is a halogen, a and b are 0 to 5 and a + b = 5) is taken, and therefore the antimony compound also has an active state in the present invention. In the above, it is considered that such mixed halogen state is adopted regardless of the starting compound.
In addition, since halogenated antimony is easily oxidized by chlorine, bromine, iodine, and fluorine from its inactive state of trivalent to its active state of pentavalent, pentavalent antimony is always used when it is introduced into the reaction system. do not have to.

Therefore, when the antimony catalyst is used in the present invention, the objective can be achieved by using trivalent or pentavalent antimony halide or antimony metal as a starting material. Therefore, specific examples of the antimony compound include antimony pentachloride, antimony pentabromide, antimony pentaiodide, antimony pentafluoride, antimony trichloride, antimony tribromide, antimony triiodide, and antimony trifluoride. Although possible, antimony pentachloride or antimony trichloride is most preferred.

In the method of the present invention, the catalyst concentration is 1,
0.1 for 1,1,3,3-pentachloropropane
-50 mol% is preferred, and 10-20 mol% is more preferred. If it is less than 0.1 mol%, the reaction rate of 1,1,1,3,3-pentachloropropane and the yield of 1,1,1,3,3-pentafluoropropane are both decreased, and if it is more than 50 mol%. The amount of tar formed of a high boiling point compound is increased, and the catalyst deterioration is remarkable, which is not preferable.

The reaction temperature is preferably 10 to 150 ° C., 5
0-130 degreeC is more preferable. Below 1 ℃, 1,1,
Reaction rate of 1,3,3-pentachloropropane, 1,1,
The yield of 1,3,3-pentafluoropropane decreases,
Further, at 150 ° C or higher, the amount of tar produced increases and the catalyst deterioration is remarkable.

The molar ratio of hydrogen fluoride to 1,1,1,3,3-pentachloropropane is preferably in the range of 5 to 30, and particularly preferably 10 to 20. If it is less than this range, the reaction rate of 1,1,1,3,3-pentachloropropane is not sufficiently high.
No improvement in the reaction rate of 3,3-pentachloropropane was observed and it is not economically advantageous in terms of recovery of unreacted hydrogen fluoride.

The pressure required for the reaction depends on the reaction temperature,
It suffices to keep the reaction mixture in the liquid phase in the reactor,
1.0 to 100 kg / cm ² is preferable, 5 to 30 kg
/ Cm ² is more preferable.

In the present invention, a solvent may coexist in the reaction system for the purpose of controlling the reaction and preventing catalyst deterioration. As the solvent, 1,1,1,3,3 which is the target product
-Pentafluoropropane may be used, or it is preferable to use a polychlorinated compound such as tetrachloroethane which is less susceptible to chlorination.

The catalyst of the present invention can be easily activated to a pentavalent activated state when it is deteriorated or when a compound other than pentavalent is used as a catalyst raw material. This method comprises 1,1,1,3,3-pentachloropropane,
Chlorine is introduced at 10 ° C to 100 ° C in the presence of 1,1,1,3,3-pentafluoropropane or any of the above-mentioned solvents. It is also possible to carry out stirring if necessary. The amount of chlorine used is 1 to 100 times the number of moles of the catalyst. At 10 ° C or lower, it takes a long time to activate, and at 100 ° C or higher, coexisting 1,1,1,3,3-pentachloropropane, 1,1,1
Chlorination of 1,3,3-pentafluoropropane or the above-mentioned solvent occurs, which is not preferable.

The method of the present invention can be carried out in a batch system, a semi-batch system or a flow system reactor in which only the product is removed from the reactor. It does not prevent a change in the reaction conditions that can be adjusted.

The reactor for carrying out the reaction of the present invention contains Hastelloy, stainless steel, monel, nickel or the like, or these metals or tetrafluoroethylene resin, chlorotrifluoroethylene resin, vinylidene fluoride resin, PFA resin or the like. It is preferable to manufacture the lining material.

1,1,1, produced by the method of the present invention
3,3-Pentafluoropropane is purified by applying a method known for fluorination reaction products, for example, hydrogen chloride, unreacted hydrogen fluoride, and liquid or gas taken out of the reactor. After that, excess hydrogen fluoride is removed by an operation such as liquid phase separation, and then an acidic component is removed with water or a basic aqueous solution, followed by distillation to obtain the desired highly pure 1,1,1,3,3,3. -It is pentafluoropropane.

[0018]

The present invention will be described in detail below with reference to examples. Example 1 A 1 l autoclave made of SUS316L equipped with a reflux condenser and a stirrer was used as a catalyst, and 0.2 mol of antimony pentachloride (6 mol) was used.
0g), 10 moles of hydrogen fluoride (200g), and 1,1,1,
1 mol (216.5 g) of 3,3-pentachloropropane was charged, and the reaction temperature was raised to 100 ° C while stirring. Although the pressure increased due to hydrogen chloride generated as the reaction progressed, when the pressure reached 15 kg / cm ² , hydrogen chloride was taken out through the reflux condenser, and then the reaction pressure was kept at 15 kg / cm ² .

After 3 hours from the start of the reaction, the reactor was cooled to room temperature and the pressure was lowered to atmospheric pressure so that the gas flowing out of the reactor was passed through an aqueous layer and then trapped in dry ice-methanol. I collected it. The collected matter and the contents of the autoclave were washed with hydrochloric acid and further washed with water, and 121.8 g of an organic substance obtained was analyzed by gas chromatography to determine the composition of the reaction product. The results are shown in Table 1.

[0020]

[Table 1]

Example 2 The same reaction as in Example 1 was carried out except that the reaction temperature was changed to 75 ° C. to obtain 129.9 g of an organic substance. The organic substances were analyzed by gas chromatography to determine the reaction product composition. The results are shown in Table 1.

Example 3 The reaction was carried out in the same manner as in Example 2 except that the amount of hydrogen fluoride was changed to 15 mol (300 g) to obtain 125.8 g of an organic substance. The organic substances were analyzed by gas chromatography to determine the reaction product composition. The results are shown in Table 1.

Example 4 128.9 g of an organic substance was obtained by carrying out the reaction in the same manner as in Example 2 except that the amount of antimony pentachloride used was 0.3 mol (90 g). The organic substances were analyzed by gas chromatography to determine the reaction product composition. The results are shown in Table 1.

[0024]

The method of the present invention has the effect that the desired 1,1,1,3,3-pentafluoropropane can be produced from the corresponding organochlorine compound in one step.

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Yasuo Hibino 2805 Imafuku Nakadai, Kawagoe City, Saitama Central Glass Co., Ltd.

Claims (3)

[Claims] 1. A liquid phase fluorination of 1,1,1,3,3-pentafluoropropane with hydrogen fluoride in the presence of an antimony catalyst. Production method. 2. The method for producing 1,1,1,3,3-pentafluoropropane according to claim 1, wherein the antimony catalyst is antimony pentahalide (halogen means chlorine, bromine, iodine and fluorine). . 3. The reaction temperature is 10 to 150 ° C., and the reaction pressure is 1.0 to 100.0 kg / cm ² , 1, 1, 1, 3, 3- Method for producing pentafluoropropane.