Synthesis of Crystalline CF3‐Rich Perfluoropolyethers from Hexafluoropropylene Oxide and (Trifluoromethyl)Trimethylsilane

Abstract The synthesis of a CF 3 ‐rich perfluoropolyether (PFPE) is achieved via the fluoride‐catalyzed reaction of hexafluoropropylene oxide (HFPO) with (trifluoromethyl)trimethylsilane (TMSCF 3 , so‐called Ruppert–Prakash reagent). Nucleophilic addition of a CF 3 anion to HFPO affords an acyl fluoride via the ring‐opening of HFPO, followed by fluoride elimination. Further addition of CF 3 anions to the acyl fluoride gives tertiary perfluoroalkoxide, which attacks HFPO to regenerate an acyl fluoride. Repetition of the sequence via substitution–polymerization affords a new PFPE as a solid, whose structure was confirmed using 19 F NMR spectroscopy, GC–MS, and MALDI–TOF MS analysis. Thermal and X‐ray diffraction analyses revealed a crystalline character. To the best of our knowledge, this is the first example of crystalline PFPE. Based on contact‐angle measurements, the critical surface tension of this solid PFPE (13.4 mN m −1 ) suggests a water‐ and oil‐repellency of this CF 3 ‐rich PFPE that is higher than that of polytetrafluoroethylene (PTFE; 18.5 mN m −1 ).