Process for the synthesis of fluorinated sulphonic acids

Abstract: Process for the preparation of a fluorinated sulphonic acid compound by hydrolysis of a corresponding fluorinated sulphonyl fluoride in the presence of a tertiary amine, comprising steps of (a) recovering a mixture of a salt of the fluorinated sulphonic acid with the tertiary amine and an ammonium fluoride salt of the tertiary amine; (b) distilling off the tertiary ammonium fluoride salt and leaving a distillation remanence containing the salt of the fluorinated sulphonic acid with the tertiary amine; and (c) recovering the fluorinated sulphonic acid compound from the distillation remanence.

Description: The present invention is directed to the preparation of fluorinated sulphonic acid compounds. In particular, the invention concerns certain improvements in the recovery of fluorinated sulphonic acid salts obtained during hydrolysis of fluorinated sulphonyl fluorides being an important step in the preparation of fluorinated sulphonic acids. The usual synthesis route of fluorinated sulphonic acids involves hydrolysis of fluorinated sulphonyl fluorides, whereby a mixture of salts comprising a fluoride salt and a salt of the fluorinated sulphonic acid is obtained. Fluorinated sulphonyl fluorides may be prepared in several ways, like electrochemical fluorination of corresponding alkane sulphonyl halides or cyclic sulphones in anhydrous HF (U.S. Patent No. 2,732,398, DE Offenlegungsschrift No. 2,725,211, DE Offenlegungsschrift No. 1,912,738, DE Offenlegungsschrift No. 4,208,364, DE Offenlegungsschrift No. 4,218,562 and DE Offenlegungsschrift No. 4,226,758). Furthermore, it is known to prepare perfluorinated sulphonyl fluorides by addition of sulphuryl difluoride or sulphuryl chloride fluoride to fluoro-olefins (GB Patent No. 1,189,562, U.S. Patent No. 2,877,267, DE Auslegenschrift No. 1,668,584, FR Patent No. 1,573,537, U.S. Patent No. 3,542,864). Hydrolysis of sulphonyl fluorides is in the known preparation processes T. Gramstad, R.N. Haszeldine, J. Chem. Soc. (1956), 173 performed by contacting the fluorides with an aqueous alkaline solution, such as solutions of KOH, NaOH or NH 4 OH. The product from the hydrolysis step is an aqueous solution of salts, from which a salt of the fluorinated sulphonic acid is recovered as a solid. Further synthesis steps involve distillation of the anhydrous salt of the fluorinated sulphonic acid by use of a strong acid such as concentrated sulphuric acid to anhydrous fluorinated sulphonic acid. Prior to distillation, fluoride ions, which are converted to HF during the distillation have to be removed because of the corrosive nature of HF. Removal of fluoride ions is usually accomplished by precipitation of fluoride salts with low solubility, such as a barium salt (U.S. Patent No. 3,919,295), or extraction of fluorinated sulphonic acid salt from a mixture of salts from the hydrolysis step (U.S. Patent No. 2,732,398). In both cases, the known preparation processes involve handling of solids and drying of salts, which complicates the processes. It has now been found that preparation of fluorinated sulphonic acids is much improved, when carrying out hydrolysis of corresponding sulphonic fluorides in presence of a tertiary amine and distilling off formed tertiary ammonium fluoride salts being formed during hydrolysis. The fluorinated sulphonic acid compound may then be recovered from the residue of the distillation step. In accordance with the above finding, this invention provides a process for the preparation of a fluorinated sulphonic acid compound by hydrolysis of a corresponding fluorinated sulphonyl fluoride in presence of a tertiary amine, comprising further steps of (a) recovering a mixture a salt of the fluorinated sulphonic acid with the tertiary amine and an ammonium fluoride salt of the tertiary amine; (b) distilling off the ammonium fluoride salt and leaving a distillation residue containing fluorinated sulphonic acid salt with the tertiary amine; and (c) recovering the fluorinated sulphonic acid compound from the distillation residue. The sulphonic acid compound may finally be recovered by protonisation of the residue with a proton donating acid and distilling off the fluorinated sulphonyl acid compound from the protonized residue. Alternatively, the residue is alkalized with an alkaline solution and the tertiary amine separated from the residue prior to the protonisation. During the distillation, the tertiary ammonium fluoride salt is distilled off in form of a poly-HF salt with the formula [t-amine H] + [F(HF)n] - , where n is typically about 2. Certain poly-HF salts are more volatile than their starting tertiary amines. As an example triisooctylamine having a boiling point of 150-160°C at 27 Pa (0.2 mm Hg) is less volatile than its poly-HF salt with a boiling point of about 100°C at the same pressure, whereas the poly-HF salt of tributylamine is less volatile (BP 100-105°C at 400 Pa (3 mm Hg)) than tributylamine (BP 60-65°C at 400 Pa (3 mm Hg)). When employing tertiary amines, which form during distillation poly-HF salts with a lower boiling point, a substantially quantitative removal of fluoride salts is provided by the above process. Preferred tertiary amines are those having a boiling point over 200°C, most preferably over 250°C at atmospheric pressure. Example 1 42.2 g of a 1:1 mixture of tributylammonium perfluorobutane-1-sulphonate (CF 3 CF 2 CF 2 CF 2 SO 3 HNBu 3 ) and tributylammonium hydrofluoride (FHNB 3 ) (prepared by reaction of perfluorobutane 1-sulphonyl fluoride with less than 1 equivalent of water in the presence of an excess of tributyl amine) were distilled at 400 Pa (0.06 psi) (3 mm Hg). At a distillation temperature of 61-63°C 6.9 g of a colourless liquid (tributyl amine) were collected and at 102°C 5.1 g of tributyl amine poly-HF salt. After the distillation, 26.3 g of a brown salt (tributylammonium perfluorobutane-1-sulphonate) remained, which crystallized upon cooling. Fluoride content of the sulphonic acid salt: 0.12%. Example 2 36.7 g of a 1:1 mixture of triethylammonium perfluorobutane-1-sulphonate (CF 3 CF 2 CF 2 CF 2 SO 3 HNEt 3 ) and triethylammonium hydrofluoride (FHNEt 3 ) (prepared by reaction of perfluorobutane 1-sulphonyl fluoride with less than 1 equivalent of water in the presence of excess of triethyl amine) were distilled at 530 Pa (0.08 psi) (4 mm Hg). 8.5 ml triethylamine were trapped in a freezing trap (F content: 530 ppm). At 94-37°C 3.7 g of a clear yellow liquid were collected, which was identified as triethylamine poly-HF salt. After the distillation, 30.4 g of a dark liquid salt (triethylammonium perfluorobutane-1-sulphonate) remained. Fluoride content of the sulphonic acid salt: 0.056%. Example 3 43.1 g of a 1:1 mixture of triisooctylammonium perfluorobutane-1-sulphonate (CF 3 CF 2 CF 2 CF 2 SO 3 HN(i-Oct) 3 ) and triisooctylammonium hydrofluoride (FHN(i-Oct) 3 ) (prepared by reaction of perfluorobutane 1-sulphonyl fluoride with less than 1 equivalent of water in the presence of an excess of triisooctyl amine) were distilled at 15 Pa (0.15 mbar) leaving 20.2 g triisooctylammonium perfluorobutane-1-sulphonate with a fluoride content of 360 ppm. Additional triisooctylamine was added and distilled off at 15 Pa (0.15 mbar) leaving 17.9 g triisooctylammonium perfluorobutane-1-sulphonate as a yellow highly viscous liquid with a fluoride content of 30 ppm.

Claims: Process for the preparation of fluorinated sulphonic acid compound by hydrolysis of a corresponding fluorinated sulphonyl fluoride in the presence of a tertiary amine, comprising steps of (a) recovering a mixture of a salt of the fluorinated sulphonic acid with the tertiary amine and an ammonium fluoride salt of the tertiary amine; (b) distilling off the tertiary ammonium fluoride salt and leaving a distillation residue containing the salt of the fluorinated sulphonic acid with the tertiary amine; and (c) recovering the fluorinated sulphonic acid compound from the distillation residue. The process of claim 1, wherein the tertiary amine is selected from the group of tertiary amines forming, during distillation in step (b), poly-HF salts with a lower boiling point than the starting tertiary amine.

Inventors: HOMMELTOFT SVEN IVAR, ZAVILLA JOHN, HOMMELTOFT, SVEN IVAR, ZAVILLA, JOHN
Applicants: TOPSOE HALDOR AS, HALDOR TOPSOE A/S
Application year: 1996
Main classification: C07C309
IPC codes: C07C309, C07C303