A Systematic Study on Biobased Epoxy‐Alcohol Networks: Highlighting the Advantage of Step‐Growth Polyaddition over Chain‐Growth Cationic Photopolymerization

Abstract Vanillyl alcohol has emerged as a widely used building block for the development of biobased monomers. More specifically, the cationic (photo‐)polymerization of the respective diglycidyl ether (DGEVA) is known to produce materials of outstanding thermomechanical performance. Generally, chain transfer agents (CTAs) are of interest in cationic resins not only because they lead to more homogeneous polymer networks but also because they strikingly improve the polymerization speed. Herein, the aim is to compare the cationic chain‐growth photopolymerization with the thermally initiated anionic step‐growth polymerization, with and without the addition of CTAs. Indeed, CTAs lead to faster polymerization reactions as well as the formation of more homogeneous networks, especially in the case of the thermal anionic step‐growth polymerization. Resulting from curing above the T G of the respective anionic step‐growth polymer, materials with outstanding tensile toughness (>5 MJ cm −3 ) are obtained that result in the manufacture of potential shape‐memory polymers.