Synthesis and properties of di(polyfluoroalkyl) peroxydicarbonates

Synthesis of di(polyfluoroalkyl)peroxydicarbonates [X(CF₂) _n CH₂OC(O)O]₂, where X = H, F; n = 1, 2, 4, 6 (yield 80%) involves the step of the chloroformate formation (yield up to 93%) via the phosgenation of polyfluorinated alcohols followed by the reaction with sodium peroxide. The rate constant of monomolecular decomposition k _term was found to decrease as the polyfluoroalkyl groups were incorporated into the peroxide: it equaled 3.30 and 3.10 s⁻¹ for X = H, n = 2 and 4, respectively, and 7.36 s⁻¹ for di-n-butylperoxydicarbonate. The new peroxides are a source of the polyfluoroalkoxy radicals and nano-modifiers of the polymers to improve their heat resistance and light stability.