Polyfluoroalkyl derivatives of nitrogen. Part XXXII. The kinetics and mechanism of the copolymerisation of trifluoronitrosomethane and tetrafluoroethylene

Abstract

The rate of copolymerisation of trifluoronitrosomethane and tetrafluoroethylene at total concentrations of up to 0·6 mol l^–1 in solution in fluoro-solvents such as 1,1,2-trichlorotrifluoroethane or perfluoro-n-hexane at temperatures from –36 to 80 °C is given by k_P[CF₃NO]^3/2[C₂F₄] and, for reactions carried out in 1,1,2-trichlorotrifluoroethane, k_P is given by: k_P(l^3/2 mol^–3/2 s^–1)=(2·9 ± 0·5)× 10⁴ exp –(9660 ± 80/RT). The free-radical chain process and mechanism proposed is in agreement with the experimental results. Further evidence in support of this mechanism has been obtained by studies of the e.s.r. spectra arising from reacting mixtures of CF₃NO and C₂F₄ and from solutions of CF₃NO in various solvents. Several earlier suggestions about the mechanism are discounted.