The synthesis of alpha-methylene-gamma-valerolactone from the sustainable gamma-valerolactone is described. The radical polymerization of this monomer with varying levels of purity has been studied under both homogeneous and heterogeneous conditions. Solution and heterophase polymerization perform equally well. The heat of polymerization of the monomer has been determined by reaction calorimetry. Properties of poly(alpha-methylene-gamma-valerolactone) dispersions obtained at very different polymerization conditions are presented, including data on thermal self-initiation and copolymerization with butyl acrylate. (C) 2015 Elsevier Ltd. All rights reserved.