Preparation of Hyperbranched Polyacrylates by Atom Transfer Radical Polymerization. 2. Kinetics and Mechanism of Chain Growth for the Self-Condensing Vinyl Polymerization of 2-((2-Bromopropionyl)oxy)ethyl Acrylate

The self-condensing vinyl polymerization (SCVP) of 2-((2-bromopropionyl)oxy)ethyl acrylate (BPEA) has resulted in the formation of hyperbranched polyacrylates. The polymerization mechanism used to polymerize the BPEA was atom transfer radical polymerization (ATRP), a “living”/controlled radical polymerization. This paper details the study of the kinetics of polymerization and the growth of the macromolecule during the polymerization. The results obtained in the polymerization were compared to the theoretical predictions for SCVP. It was determined that the polymerization deviated from the ideal case, as a consequence of the establishment of a dynamic equilibrium in ATRP resulting in the addition of more than one monomer unit in a single activation step.