Expanding the polymerization potential of itaconic acid through methacrylate functionalization

Abstract

Itaconic acid (IA) is a bio-renewable molecule with increasing industrial availability. However, IA-based polymers have been limited by low molecular weights and conversions. In this work, we report the synthesis of two novel methacrylate-functionalized IA monomers. Using various reversible-deactivation radical polymerization methods, we achieved well-defined polymers with high conversions (≥98%) and moderate reaction times (e.g., 70 minutes by atom transfer radical polymerization at 80 °C). Homopolymers of these two monomers exhibited a range of properties, with glass transition temperatures (T_g) ranging from −40 °C for heptyl-functionalized moieties to 14 °C for benzyl-functionalized moieties. Controllable reaction kinetics enabled the synthesis of pre-designed AB-type diblock copolymers, demonstrating the potential of the heptyl-functionalized moiety as a soft block in phase-separated materials. The favorable reaction kinetics of these methacrylate-functionalized IA monomers make this approach one of the most promising pathways for incorporating renewably sourced IA into polymeric materials.