A DFT study on the molecular mechanism of the conjugated nitroalkenes polymerization process initiated by selected unsaturated nucleophiles

Abstract

The participation of the nitroethene and its α-substituted analogs as model nitrofunctionalized monomers, and (Z)-C,N-diphenylnitrone and methyl vinyl ether as initiators in the polymerization reactions, has been analyzed in the framework of the density functional theory calculations at the M06-2X(PCM)/6-311 + G(d) level. Our computational study suggests the zwitterionic mechanism of the polymerization process. The exploration of the nature of critical structures shows that the first reaction stage exhibits evidently polar nature, whereas additions of further nitroalkene molecules to the polynitroalkyl molecular system formed should be considered as moderate polar processes. The more detailed view on the molecular transformations gives analysis based on the bonding evolution theory. This study shows that the case of polymerization reaction between nitroethene and (Z)-C,N-diphenylnitrone allows for distinguishing eleven topologically different phases, while, in the case of polymerization reaction nitroethene and methyl vinyl ether, we can distinguish nine different phases.