Characterization of the telomerization reaction path for vinylidene fluoride with ĊCl3 radicals

Abstract

Radical telomerization of fluorinated olefins is a very stimulating model to study polymerization of fluorinated polymers. An active experimental research program has been thus developed so far. To supplement these data molecular modelling is mostly appropriate. We thus propose an ab initio calculation and Density Functional Theory (DFT) approach, to study competition between propagation and transfer steps during the telomerization reaction of the vinylidene fluoride (VDF) with ĊCl₃ radicals. Three chain transfer agents Cl₃C–Z (Z = H, Cl, Br) have been considered. The most probable reaction pathways have been determined, and the transfer constants (C_T) were thereafter calculated. A very linear correlation between the experimental and simulated data was obtained, revealing the correctness of the proposed approach.