Perfluopolyether (PFPE) (poly)diacyl peroxides: synthesis and applications

This paper deals with the synthesis of perfluoropolyether (PFPE) (poly)diacyl peroxides with mean EWs ranging from 500 to 4000 g eq.−1 via H2O2 and base from the corresponding PFPE diacyl halides, their decomposition (thermal and hydrolytic) and the synthesis of the corresponding di-halides by the reaction with elemental halides. A great advantage of this novel synthesis over other synthetic approaches is the ease in obtaining polyperoxides containing up to at least two diacyl peroxide groups/chain. This property confers to these peroxides a greater thermal stability. The synthesis of PFPE diacyl peroxides and its dependence on contact times of reagents, solvent, reaction temperature and reagent concentrations will be presented and discussed. Data concerning the thermal and hydrolytic decomposition of these PFPE diacyl peroxides as well as the dependence of their homolytic decomposition kinetics on EW will also be presented and discussed. Interestingly, we have discovered that these PFPE (poly)diacyl peroxides could in turn be easily available precursors of the corresponding α-ω-iodides or bromides.