Effect of Multifunctional Initiator on Self-Condensing Vinyl Polymerization with Nonequal Molar Ratio of Stimulus to Monomer

Abstract

This work theoretically dealt with the effect of multifunctional initiators on the self-condensing vinyl polymerization (SCVP) with nonequal molar ratio of stimulus to monomer (α). The molecular size distribution function and other molecular parameters of the resulting hyperbranched polymers were derived analytically. The feed ratio of stimulus to monomer significantly affects the molecular parameters of the products. At the specified conversion of monomer (x), 99%, the number distribution curve of the total species formed appears as a bimodal structure for the low stimulus-to-monomer ratio, and it changes from bimodal to monomodal with increasing fraction of stimulus. When the polymerization is completed, the polydispersity index of the product increases with increasing α value, which is opposite for the polymerization without the core initiator. The higher the functionality of the core initiator (f), the lower the polydispersity index. However, unlike the homo-SCVP with core initiator, the polydispersity index does not always monotonously decrease with increasing fraction of core initiators (β). If β > √α/f, then it increases with increasing β; otherwise, it decreases monotonously.