Synthesis and characterization of poly(tetrafluoroethyleneperoxides)

Tetrafluoroethylene (TFE) and oxygen react at low temperature in radical conditions to give perfluoropolyether–polyperoxide polymers. This oxypolymerization reaction has been applied on industrial scale for the manufacture of perfluoropolyethers, presently used in many application fields. known that highly unstable polymers containing large amounts of peroxidic units –CF2CF2OO– can be formed in particular conditions and may represent a potential hazard in the TFE oxypolymerization process. However little has been reported in the literature on the reaction conditions and the characterization of these polymers. present paper we describe the synthesis of perfluoropolyether–polyperoxide polymers with high peroxide content up to the nearly pure poly(perfluoroethyleneperoxide). The investigation is particularly focused to elucidate the relationship between reaction conditions, kinetics and polymer structure. The experimental results indicate that the physical chemical properties of these materials are strongly affected by the peroxide content, this latter depending on the reaction conditions, mainly TFE concentration and initiation rate.