Peroxidic perfluoropolyether from tetrafluoroethylene oxidation: micro structural analysis by NMR spectroscopy and mechanistic considerations

The oxypolymerization reaction of tetrafluoroethylene gives peroxidic perfluoropolyethers of formula:(CF2CF2O)m(CF2O)n(CF2CF2OO)p(CF2OO)qwhich are key intermediates for the manufacture of PFPE oils and derivatives. 19F and 13C NMR spectroscopy has been used for the systematic micro structural analysis of the above polymer, as a function of the peroxide content. The results of this investigation, particularly focused on the peroxidic sequences, have been discussed in terms of reaction mechanisms and kinetics.