PROCESS FOR PRODUCING 1,1,2,2,3-PENTAFLUOROPROPANE

Abstract: A process for producing 1,1,2,2,3-pentafluoropropane in a high yield industrially and economically by reacting 1-chloro-2,2,3,3-tetrafluoropropane with hydrogen fluoride in the presence of a fluorination catalyst.

Description: This invention relates to a method of producing 1,1,2,2,3-pentafluoropropane. Prior art 1,1,2,2,3-pentafluoropropane (indicated as R-245ca hereafter) is utilized for blowing or cleaning solvent or a heat medium as a substitute for CFC and HCFC. It is especially useful as a urethane blowing agent. As a method of preparing R-245ca, a process using a chemical reaction by the following formula by Walter et al. is known (J.A.C.S. , 77 , 4899 (1955) ). Hc 2 F 4 CH 2 OSO 2 C 6 H 5 +KF diethylene glycol / HC 2 F 4 CH 2 F However, this reaction is not suitable for industrial use due to a low yield, complicated operation, treatment for KCl after the reaction, generated by use of KF, and high cost. On the other hand, according to a method described in U.S.P. 2,980,740, R-245ca is synthesized by reacting 2,2,3,3-tetrafluoropropanol with SF 4 . But this method is not suitable for industrial use either, because a low yield around 65% is obtained, SF 4 is intensely poisonous as strong as phosgene, and the operation is complicated. WO-A-90 08754 discloses a method for preparing 1-chloro-2,2,3,3-tetrafluoropropane including the steps of producing 2,2,3,3-tetrafluoropropanol from tetrafluoroethylene and methanol, then reacting it with sulfuryl chloride to obtain a chlorosulfonic acid ester. and then reacting it with an alkali metal chloride. As mentioned above, a reaction example for R-245ca suitable for industrial manufacturing is not found at present. Object of the invention An object of this invention is to provide a manufacturing method suitable for industrial use which enables to produce R-245ca at high selectivity, high yield, good operationability and low cost. Construction of the invention As a result of repeated eager study by the inventors to aim at an industrial production method for R-245ca by fluorinating 1-chloro-2,2,3,3-tetrafluoropropane (indicated as R-244ca hereafter), they found that R-245ca can be produced at high selectivity by a method comprising the steps of reacting 2,2,3,3-tetrafluoropropane-1-ol with thionyl chloride in the presence of active carbon to obtain 1-chloro-2,2,3,3-tetrafluoropropane. and then reacting the 1-chloro-2,2,3,3-tetrafluoropropane with hydrogen fluoride in the presence of a fluorinated catalyst. Catalysts used in the reaction of this invention are fluorinated catalysts, for example, there can be used metal fluorides and / or metal oxyfluorides produced by fluorinating a metal oxide, with HF separated from a solution of a metal salt by the use of alkali, for example. In this case, hydrochloride and nitrate can be used as the metal salt. And, ammonia, carbamide, and metal hydroxide can be used as the alkali. Besides, for a method of obtaining chromium oxide, a method of obtaining it by reducing CrO 3 can be adopted, and for a method of obtaining the chromium oxyfluoride, a method of treating CrF 3 (nH 2 O) with oxygen under heating can be adopted. For the metals used, one kind of or a mixture of two or more kinds of metals selected from alminium, chromium, manganese, nickel and cobalt can be used. Those metal fluorides can be supplied by themselves, as well as carried on suitable carriers. For the carriers, e.g. active carbon or fluorinated aluminium can be used. The reaction temperature can be adequately chosen from the range of 250 to 450 °C, but a too low temperature is not practical due to a slow reaction. The reaction temperature is desirably from 300 to 400 °C. An excess ratio of HF to R-244ca can be selected adequately from the range of 1 to 100 according to the objective conversion rate, the rate of the product, the contact times and the reaction temperature. That is, HF to R-244ca may be from 1 : 1 to 100 : 1. However, although the reaction can be carried out even if the excess ratio of HF is over 100, the productivity decreases not to be practical. The yield of the target product can be raised by refluorinating the raw material returned to a reactor after separating necessary components from the reaction product. Possibility of utilizing the invention in industry The production method of this invention is suitable for the industrial use, because the economical HF is used, R-244ca can be continuously fluorinated by gaseous phase reaction, and the selectivity and yield of the product can be improved. Embodiments The invention will be explained in the following examples which can be variously modified on the basis of the technical concept of this invention. 〈Preparation example 1〉 Chromium hydroxide prepared from aqueous chromium nitrate and aqueous ammonia was separated by filtering, washed with water, dried at 100 °C, then molded into cylindrical shape having a diameter of 3mm and a hight of 3mm by a tapping-type molding machine. The thus obtained catalyst was filled in a Hastelloy C-made reaction tube and heated to be kept at 400°C for 1 hour under nitrogen flow. Then, the temperature was lowered to 200 °C and hydrofluoric anhydride was supplied to treat the catalyst for 1 hour to activate. Operation example 1 10cm 3 of the catalyst obtained in Preparaiton example 1 was filled in a reaction tube and the reaction temperature was controlled at 350 °C, and then 200cm 3 of HF and 35cm 3 of R-244ca were introduced in gaseous state. R-244ca used here was prepared by the following steps: 20cm 3 of active carbon was filled in a Hastelloy C-made reaction tube and treated at 300°C for 2 hours under nitrogen flow. Then the temperature was lowered to 200°C, HCF 2 CF 2 CH 2 OH and SOCl 2 were introduced into the reaction tube respectively at 26.4 g/hr and 24 g/hr as supply rate. The product was removed at a water-washing column and then recovered in a cold trap cooled with water. R-244ca was obtained by rectification and separation of the recovered organic compound. The product was washed with water and then analyzed by gas-liquid chromatography (GLC). The result is shown in the following table-1. In this table-1, 2,3,3-trifluoro-1-propene is indicated as R-1243, 1,2,3,3-tetrafluoro-1-propene as R-1234 and 1-chloro-2,3,3-trifluoropropene as R-1233. The condition of GLC analysis : PORAPACK-Q 3m. Under temperature elevated at 10°C/min from 100 °C. R-1243 2.6% R-1234 0.8% R-245ca 66.2% R-1233 0.5% R-244ca 29.9% According to this result, it is understood that the reaction based on this invention can bring about an easy production of the objective R-245ca at high selectivity and is suitable for the industrial use. 〈Preparation example 2〉 A catalyst was prepared under the same condition as that of Preparation example 1 except for changing chromium nitrate used in Preparation example 1 to a mixture of aluminium nitrate and chromium nitrate (1 : 1 of mole ratio). Operation example 2. A reaction was carried out under the same condition as that of Operation example 1 except for using the catalyst obtained in Preparation example 2. The result of GLC analysis is shown in the following table-2. R-1243 2.4% R-1234 0.7% R-245ca 35.2% R-1233 0.5% R-244ca 61.2% This result also shows that in the reaction according to this invention the target product can be obtained at good selectivity.

Claims: A method of producing 1,1,2,2,3-pentafluoropropane comprising the steps of reacting 2,2,3,3-tetrafluoropropane-1-ol with thionyl chloride in the presence of active carbon to obtain 1-chloro-2,2,3,3-tetrafluoropropane, and then reacting the 1-chloro-2,2,3,3-tetrafluoropropane with hydrogen fluoride in the presence of a fluorinated catalyst. The method as defined by claim 1, in which the fluorinated catalyst is a fluoride and/or oxyfluoride obtained by fluorinating an oxide of one kind of or two or more kinds of metals selected from the group consisting of aluminium, chromium, manganese, nickel and cobalt with hydrogen fluoride. The method as defined by claim 1 or 2, in which the reaction temperature is in the range from 250 to 450°C. The method as defined by any of claims 1-3, in which hydrogen fluoride is contacted with 1-chloro-2,2,3,3-tetrafluoropropane in a mole ratio from 1/1 to 100/1.

Inventors: AOYAMA HIROKAZU, SEKI EIJI, YAMAMOTO AKINORI, YASUHARA TAKASHI, AOYAMA, HIROKAZU, SEKI, EIJI, YAMAMOTO, AKINORI, YASUHARA, TAKASHI, AOYAMA, HIROKAZU, YODOGAWA WORKS OF, SEKI, EIJI, YODOGAWA WORKS OF, YAMAMOTO, AKINORI, YODOGAWA WORKS OF, YASUHARA, TAKASHI, YODOGAWA WORKS OF
Applicants: DAIKIN IND LTD, DAIKIN INDUSTRIES, LIMITED
Application year: 1993
Main classification: C07C19
IPC codes: C07C17, C07C19