Monomer reactivity in functionalized vinyl copolymers: A theoretical approach

This work studies how the variation of the inter-atomic distance affects the total energy in addition reactions of several vinyl radicals on vinyl monomers. Based on the energetic profiles obtained, the corresponding activation eneigies were evaluated and correlated with the relative reactivity of the monomers forming the vinyl copolymers poly(2-vinylpyridine-co-N-vinyl-2-pyrrolidone), poly(4-vinylpyridine-co-N-vinyl-2-pyrrolidone), poly(vinyltrimethylsilane-co-N-vinyl-2-pyrrolidone) and poly(vinylcyclohexane-co-N-vinyl-2-pyrrolidone), previously characterized with an estimation of their monomer reactivity ratios (MRR). The results are discussed as a theoretical support to a work developed in the general framework of the synthesis and characterization of functionalized vinyl copolymers.