Catalytic process for phospho-halogenation of fluorinated alcohols
View Patent ↗A process for manufacturing a polyfluroalkanoyl phosphorodichloridate comprising reacting a polyfluoroalkanol having the general formula R f —CH 2 —OH, wherein R f is a linear or branched C 1 -C 8 perfluoroalkyl group optionally interrupted by O, with at least 4 moles of POCl 3 per mole of R f —CH 2 —OH in the presence of 0.1 to 0.2 moles of LiCl catalyst per mole of R f —CH 2 —OH at a temperature between 95° C. and 110° C. to form a phosphorodichloridate of the general formula R f —CH 2 —O—P(O)Cl 2 .
1. A process for manufacturing a polyfluoroalkanoyl phosphorodichloridate having the formula R f —CH 2 —O—P(O)Cl 2 , said process comprising:
reacting a polyfluorinated alkanol having the formula R f —CH 2 —OH, wherein R f is a linear or branched C 1 -C 8 perfluoroalkyl group optionally interrupted by O, with at least 4 moles of POCl 3 per mole of R f —CH 2 —OH in the presence of 0.1 to 0.2 moles of LiCl catalyst per mole of R f —CH 2 —OH at a temperature between 95° C. and 110° C. to form a polyfluoroalkanoyl phosphorodichloridate of the formula R f —CH 2 —O—P(O)Cl 2 , wherein the molar ratio of polyfluoroalkanoyl phosphorodichloridate to byproduct polyfluoroalkanoyl phosphorochloridate is at least 10 to 1.
2. The process according to claim 1 , wherein said polyfluorinated alkanol is selected from the group consisting of pentafluoropropanol, heptafluoro-1-butanol, 2,3,3,3-tetrafluoro-2-(heptafluoropropoxy)-1-propanol, and 2,5-di(trifluoromethyl)-3,6-dioxa-1H,1H-perfluoro- l -nonanol.
3. The process according to claim 1 , wherein said polyfluorinated alkanol is reacted with 4 to 8 moles of POCl 3 per mole of polyfluorinated alkanol.
4. The process according to claim 1 having a yield of polyfluoroalkanoyl phosphorodichloridate of at least 50%.
5. The process according to claim 4 having a yield of polyfluoroalkanoyl phosphorodichloridate of at least 75 wt %.