Network Dimension Theory and Its Application to Miniemulsion Vinyl/Divinyl Copolymerization

Newly developed network dimension theory is used for rapid estimation of the root-mean-square radius of gyration of each polymer molecule formed during vinyl/divinyl copolymerization. The -value is used for describing the enhancement of intramolecular crosslinking or the cyclization reactions. The model is applied to the miniemulsion copolymerization, and both conventional free-radical polymerization and ideal living polymerization are considered. Some of important characteristics of network architecture formed in these two types of polymerization mechanisms that cannot be predicted based on the classical chemical kinetics can be reproduced by the model successfully. For example, such unique characteristics as the pendant double bonds are consumed from the start of polymerization in conventional free-radical polymerization but not so in living polymerization can be elucidated. The present kinetic model provides useful insights into the size- and structure-dependent network formation. Keywords: Crosslinking, Emulsion polymerization, Gelation, Graph diameter, Radius of gyration