Kinetic Study of Self-Condensing Vinyl Polymerization via ATRP: A Stochastic Model Coupled with Ab Initio Calculations

Self-condensing vinyl polymerization (SCVP) via atom transfer radical polymerization (ATRP) is a practical approach for synthesizing hyperbranched polymers with highly branched structures, low dispersity, and high end-group functionality. In this work, a modeling study of SCVP–ATRP has been performed, focusing on the kinetics, dispersity, functionality, and topological parameters. Meanwhile, ab initio calculations were used to differentiate the activation and deactivation reactivities of various functional groups. The simulation results were in agreement with the reported experimental data. The study highlighted that the activation–deactivation equilibrium significantly reduces the number of active centers and suppresses termination reactions, and the cyclization initiation and propagation confine polymer–polymer reactions, thereby avoiding gelation and controlling dispersity and functionality. Moreover, the effects of different group deactivation rate coefficients and inimer structures on hyperbranched polymerization were also investigated. The current work will be expected to guide the rational structural design of inimers and ligands.