A computational approach to the polymerizabilities of diallylamines

Some selected diallylamine monomers have been studied with the semiempirica l PM3 method as model compounds for N,N-dialkyl-N-2-(alkoxycarbonyl) allyla mmonium salts, in order to build up a quantitative and qualitative relation ship between the experimental cyclopolymerizabilities of the monomers and c alculated parameters such as charge, energy, geometrical features, bond ord ers, local softness values and HOMO-LUMO gaps. The charges on nitrogen, vin yl and allyl carbons, the activation barriers, the local softness values an d the HOMO-LUMO gaps are found to represent the polymerizability trend of t he monomers in general. Three-dimensional structures have been proposed for the reactants and their transition states by geometry optimizations with P M3.