The preparation of primary poly-hexafluoropropylene oxide halides (poly-HFPO-CF2X where X = I, Br, Cl and F)

Perfluorinated polyethers (PFPEs) are an important class of chemicals in industry due to their outstanding thermal stability, chemical inertness, and low vapor pressure. Since the first report on the polymerization of hexafluoropropylene oxide, there have been many papers on functionalized PFPEs. We have found that the reaction of poly-hexafluoropropylene oxide (HFPO) acid fluoride with LiI leads, to first the secondary and subsequently, to the primary poly-HFPO iodide. The primary poly-HFPO iodide, like perfluoroalkyl iodide, should provide the starting point for many new products. In this paper, from the primary poly-HFPO iodide we have prepared the family of primary poly-HFPO halides (X = I, Br, Cl and F). Their spectral data are discussed.