TW200535125A - Process for preparing perfluoroalkanesulfonyl fluoride - Google Patents

Abstract

A process for preparing a perfiuoroaikanesuifonyl fluoride represented by the general formula: Rf-CF2-SO2F wherein Rf represents F, CF3 or C2F5, comprising reacting a monohydroperfLuoroaikanesulfonyi fluoride represented by the general formula: Rf-CHF-SO2F wherein Rf is as defined above with fluorine or a fluorine-containing gas.

Description

200535125 (1) 发明 Description of the invention [Technical field to which the invention belongs] The present invention relates to a method for producing perfluorinated alkanesulfonium fluoride, and particularly to the intermediates used when persulfonated sulfonic acid and its synthetic salts Product (S. Benefice-Malouet, H. Blanc et al.'J. Of Fluorine

Chemistry, 3 1 (1 986), 3 1 9.3 3 2), or as raw materials for perfluorinated alkanesulfonimines and their synthetic fluorenes (U.S. Pat. No. 5,072,040, December 10, 1991 ), Or a variety of perfluorinated alkanesulfonyl fluoride (PF AS F) used as a cleaning gas component with high-speed etching, namely methanesulfonium trifluoride, sulfonium fluoride , And a method for producing sulfonium fluoride of propylene oxide. [Prior art] The known manufacturing method of pentanefluorin sulfonium fluoride and isopropylsulfonium fluorination (U.S. Pat. No. 3,542,864, November 24, 1970) is in the solvent, fluorine In the presence of chemistry, 60 hours at 110 ° C will allow the necessary olefins and S02F2 to interact with each other. Because the equipment of this method is complicated, and the use of expensive fluorinated planers produces waste that is toxic and difficult to reuse, it has not been developed afterwards. In the industrial field, perfluorinated alkanesulfonium fluoride is a sulfur-containing halogen that will be placed on a nickel anode by the SIMONS method (in the presence of sodium fluoride in anhydrous hydrogen fluoride at a temperature of 10 to 17 ° C). Hydrocarbon-paraffin sulfonium chloride 'method for fluorinating it by electrochemistry, with a synthesis rate of 79-85%, Brice, Trott, US Patent No. 2 73 23 98, 1954; T. Gramstad, 200535125 (2) RNHaszeldine, J. of Chem. Soc. London, 1957, p. 2640-2645). However, the productivity of the electrolytic grain is not always fixed, that is, it increases in the initial stage of electrolysis, and after a short period of time after stabilization, the corrosion of the anode and the anode rapidly decrease due to the adhesion of resinous products. Therefore, the above mentioned 7 9 ~ The synthesis rate of 85% does not mean that the entire process remains constant. The formation of a large number of by-products also reduces the efficiency of fluorine and power use, and it is difficult to separate the target products. In addition, it is mixed with hydrogen fluoride (HF), and separation from HF is a difficult subject in itself. The target product cannot be separated by methods other than rectification. I tried to use other raw materials (alkyl sulfonyl alkyl ether or alkyl sulfonyl alkyl sulfonamide) to increase the current and efficiency of fluorine, but it could not eliminate the process instability and resin formation. At the same time, the raw materials were not easy Obtained (HAVogel, JCHansen, U.S. Patent No. 5,468,261, 1 994). A known manufacturing method other than fluorination by electrolytic method is to obtain a perfluorinated alkanesulfonium fluoride by reacting a hydrocarbyl-containing alkanesulfonium fluoride and a fluorine gas (Kanto Denki Chemical Co., Ltd. 2003-206272) 'This method produces a by-product of hydrofluorinated alkanesulfonium fluoride in which a part of hydrogen atoms and fluorine atoms are replaced by many hydrocarbon groups, so the synthesis rate of PFASF in which all hydrogen atoms and fluorine atoms are replaced is low (12%). [Summary of the Invention] The subject of the present invention, 'In order to obtain a target product with a high synthesis rate, use commercially available industrial raw materials and a standard that generates less waste. 200535125 (3) Production technology to develop and replace electrochemical methods pF A SF manufacturing method. In order to solve the above problems, the present invention provides, by way of example, the following methods [1] to [5]. [1] A method for producing a perfluorinated alkanesulfonyl fluoride represented by general formula (2), which is characterized by the following formula ^ (1 plant Rf-CHF-S02F ⑴ (where Rf represents F, cf3, or c2F5) is a monohydroperfluorinated alkanesulfonium fluoride, which reacts with fluorine or a fluorine-containing gas,

Rf-CF2-S02F (2) (In the above formula, 'Rf is the same as the aforementioned regulation). [2] The method of item [1] according to the disclosure of the invention, wherein the reaction of the compound represented by the general formula (1) with fluorine or a fluorine-containing gas is performed at a temperature of 0 to 30 ° C. [3] As Disclosure of the invention The method of item [1], wherein the compound represented by the general formula (1) is a product obtained by hydrolysis of a perfluorinated alkane sultone. [4] The method according to [3] of the disclosure of the invention, wherein the perfluorinated alkane sultone 'is obtained by reacting a perfluoroolefin with anhydrous sulfuric acid. [5] The method of item [4] according to the disclosure of the invention, wherein the reaction of perfluoroolefin with sulfuric acid without 200535125 (4) is carried out at a temperature of 45 to 85 ° C. [Embodiment] For the method of the present invention, for example, perfluoroolefin (PFO), which is an essential raw material compound, is placed at a temperature of 35 to 85 ° C, and the most ideal temperature is 4 5 to 6 5 ° C. Time 1 2 ~ 3 2 hours. Perfluoroalkane sultone (PFAS) synthesized by reaction with anhydrous sulfuric acid. Monohydroperfluoroalkanesulfonium fluoride (MHPFASF) obtained after hydrolysis, at 0 ~ 30 t: temperature In this case, the most ideal temperature is 20 ~ 30 ° C. After adding fluorine and fluorine-containing gas, fluorination is generated, so the perfluorinated alkanesulfonium fluoride is obtained. This process is illustrated by the following reaction formula.

Rf-CF--CF2i ^ Rf-CF-CF2J ^ Rf-CFH-S〇2FJ ^ Rf-CF2-S02F 02S-0 Here, the substances represented by Rf are the same as the aforementioned regulations. In order for the hydrolysis to proceed successfully, the set temperature is based on the physicochemical constant of the hydrolyzed perfluorinated alkanelactone, which is set at the boiling point of the perfluorinated alkanelactone plus 3 3 ° C, but Not a decisive important variable. In order to replace the last hydrogen atom in alkanesulfonium fluoride, the process of fluorination with fluorine element has never been performed before, and it has not been disclosed in the literature that we know. This process is carried out with fluorine element. During the fluorination stage, it was placed in the above temperature range (0 ~ 30 ° C), and the decomposition of the fluorinated product did not obviously form 200535125 (5), and the maximum synthesis rate of the target product was 87.5%. In order to remove the hydrogen fluoride formed at the same time after the fluorination, the mixture is washed with an alkaline aqueous solution and dried with zeolite or silica gel, and must be subjected to rectification if necessary. All reagents used are industrial products that can be obtained. Byproducts produced during the hydrolysis stage can be used in the manufacture of various chemical substances. Moreover, the solvent related to the present invention is not particularly necessary, and an inert solvent may be used in the reaction. The following examples illustrate the invention. Example 1 Synthesis of perfluorinated propane sultone. In a steel reactor (type of steel 12X18H10T) with a capacity of 2 liters, which had been equipped with a steel film for heating and a connection tube for reagent discharge, 492 g (3 · 28 mol) perfluorinated propane and 256 g (3.2 mol) of S03, the reactor was heated to 85 ° C, kept in this state for 12 hours, after cooling to room temperature, excess perfluorinated propane was removed to obtain 693 g (3 moles) of perfluoropropane sultone with a synthesis rate of 9 1.9%. Synthesis of monohydroperfluoroalkanesulfonium fluoride In a 2 liter flask equipped with a stirrer, reflow cooler and titration funnel, 550 grams of water (equivalent to 10 times excess) Amount) 'At a temperature of 0 ~ + 1 ° C, while vigorously stirring 693 grams of perfluoropropane sultone', slowly pour it in, and judge the water from the point at which gas generation stops. -10- 200535125 (6) Solution Whether the reaction is over. In order to maintain the necessary temperature level, for example, the flask can be placed in the refrigerant slag, or the refrigerant can be supplied in the cooling coil to cool the reactants. Any known method can be used arbitrarily. After the reaction was completed, two layers were formed. The lower layer containing monohydroperfluoroalkanesulfonyl fluoride (MHPFESF) was separated and dried with zeolite. Therefore, 48.8 g (2.65 mol) of dried MHPFESF was obtained, which is equivalent to 88. % Synthesis rate.

Examples 2 and 3 The various conditions in Example 1 were changed to Table 1, and as Examples 2 and 3, each of them was synthesized using perfluoroethylene and perfluorobutene as starting materials to synthesize individual monomers. The synthesis rates of the obtained products are shown in Table 1 for hydrogen perfluorochain methanesulfonyl fluoride (MHPFMSF) and monohydroperfluoropropanesulfonyl fluoride (MHPFPSF).

-11-200535125 毖 毖 feeding yield (%) i 95.0 1 81.0 I temperature (° c) 0 ~ + 1 ί IIT— + 1 〇S u- ^ ί ί 4n CL S 工 Ρη tight 2 S 320 I 302 water Weight (g) 430 290 m ili Weight of raw material PFAS (g) 430 I 445 1 Name of MHHPFA SF to be synthesized MHHPFA SF Monohydroperfluoro chain methanesulfonyl fluoride (MHPFM SF) Monohydroperfluoro! Propanesulfonium sulfonium (MHPFP SF) Name of raw material PFAS Perfluoroalkane lactone Perfluorobutane lactone Perfluorinated alkane lactone Synthesis Synthetic Variable 1 | Time (hr) CNJ CNJ CM CO Temperature (° c) JO Yield (%) 94.8 97.8 Weight of combined PFAS 9_ 430 II 445 1 Weight of anhydrous sulfuric acid g 202 130 Weight of raw PF0 g 252 II 325 Name of synthesized PFAS Name of ene lactone raw material PF0 Perfluoroethylene — | Perfluorobutene «㈣ S CM C0 -12-200535125 (8) Example 4 Flow type MHPFESF fluorinated steel bubbler with 2 liter capacity (Steel type 12X1 8H10T), force into 170 grams of MHPFESF, heat to 40 ° C, 5 kilometers per hour At this time, the ratio of MHPFESF to nitrogen is 1: 3 (molar ratio), and the mixed gas of nitrogen and MHPFESF is supplied to a steel reactor heated to 3 ° C (type of steel 12X18H10T , Length 1 800mm, diameter 45mm), supply fluorine gas with a ratio of MHPFESF to fluorine mole ratio of 1: 0.95 in the same reactor. Pass the reaction product through a 5% by weight KOH aqueous solution, dry with silica gel, and collect In a trap below -78 ° C, 163.3 g of perfluoroethanesulfonium fluoride (PFESF) was obtained, and the synthesis rate of the target product was 87.5%. Example 5 MHPFESF fluorination in a static mode The fluorination is carried out in a steel pressure cooker (steel type 12X18H10T) with a capacity of 2.5 liters. Put 18.5g of MHPFESF in the pressure cooker, and supply MHPFESF to fluorine mole ratio at 30 ° C: 1.03 6 of fluorine gas. After the mixture is kept for 24 hours, it is neutralized with a 5% by weight KOH aqueous solution and dried with silicone to obtain 17.7 grams of £ 3, which is equivalent to a synthesis rate of 87.2%. Examples 6 to 19 -13-200535125 in Example 4 (flow method) or Example 5 (static method) (9) Raw materials, reaction temperature, raw materials, mole ratio to fluorine, and reaction method The synthesis was changed to the conditions shown in Table 2 and the synthesis rate of the obtained product is also shown in Table 2.

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Lox— 91, ZV-8T— 6V- 15 200535125 (11) Industrial applicability It can be seen from the results of the above-mentioned embodiments that the PFA SF manufacturing method of the present invention uses standard production techniques and possible acquisitions. Raw materials, to ensure the high synthesis rate of the target product, give the possibility of implementing this method under industrial conditions. This method is different from the fluorination of electrochemical methods. This method can ensure the stability of engineering time and significantly reduce power consumption.

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Claims (1)

200535125 (1) Scope of patent application 1 · A method for producing a perfluorinated alkanesulfonium fluoride represented by general formula (2), which is characterized by the following general formula (1): ⑴ Rf-CHF-S02F ( (In the above formula, Rf represents F, CF3, or C2F5) The monohydroperfluorinated alkanesulfonium fluoride shown is formed by reacting with fluorine or a fluorine-containing gas, (2) Rf-CF2-S02F (wherein Rf is the same as the foregoing regulation). 2. The method according to item 1 of the scope of patent application, wherein the reaction of the compound represented by the general formula (丨) with fluorine or a fluorine-containing gas is performed at a temperature of 0 to 30 ° C. 3. The method according to item 1 of the scope of patent application, wherein the compound represented by general formula 0) is obtained by hydrolysis of a perfluorinated alkane sultone. 4. The method according to item 3 of the scope of patent application, wherein the perfluorinated bond sultone is obtained by the reaction of a perfluoroolefin with anhydrous sulfuric acid. 5. The method of applying the IPG patent to the 4th sibling, where the reaction of anhydrous sulfuric acid is carried out at a temperature of 4 5 ~ 8 5 t. -17- 200535125 柒, (a) (two), the designated representative map in this case is: None, simple description of the element representative symbols of this representative map: Μ 捌, if there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: