Reactivity Study of Elementary Steps in the Polymerization Mechanism of Acrylfuranic Compounds by Frontier Molecular Orbital Theory

Abstract

A reactivity study of the most important elementary steps (propagation, intermolecular degradative transfer, and re‐initiation) in free‐radical polymerization of acrylfuranic systems, furfuryl acrylate (FA), and furfuryl methacrylate (FM), using the frontier molecular orbital theory is described. A qualitative explanation of reactivity trends of these steps for both systems is given based on absolute values of the SOMO/HOMO gap. The small difference between values of kp for FA and FM compared to that found for MA and MMA (${{k_{{\rm p}}^{{\rm (FA)}} } \mathord{\left/ {\vphantom {{k_{{\rm p}}^{{\rm (FA)}} } {k_{{\rm p}}^{{\rm (FM)}} }}} \right. \kern-\nulldelimiterspace} {k_{{\rm p}}^{{\rm (FM)}} }}< {{k_{{\rm p}}^{{\rm (MA)}} } \mathord{\left/ {\vphantom {{k_{{\rm p}}^{{\rm (MA)}} } {k_{{\rm p}}^{{\rm (MMA)}} }}} \right. \kern-\nulldelimiterspace} {k_{{\rm p}}^{{\rm (MMA)}} }}$) is justified semi‐quantitatively by applying a formulation for the change of energy in the transition state using second‐order perturbation theory.magnified image