Influence of polymerization procedure on polymer topology and other structural properties in highly branched polymers obtained by A2 + B3 approach

Computational studies were carried out to investigate the influence of polymerization procedure on the topology and various macromolecular characteristics of the highly branched polymers formed by the reaction of A2 and B3 type monomers through step-growth polymerization reactions. The influence of three different polymerization procedures on the properties of the polymers formed was investigated, namely, (i) slow addition of A2 over B3, (ii) slow addition of B3 over A2, and (iii) mixed A2 + B3. Topology, degree of branching, number and weight average molecular weights, and polydispersity index of the polymers were determined using Monte Carlo simulations, assuming different levels of cyclization ratios during the reactions. Interestingly model polymers obtained by the slow addition of B3 over A2 produced much higher degree of branching or truly hyperbranched polymers, when compared with the other two methods, which mainly resulted in linear growth with slight branching.