Photoiniferter‐RAFT Polymerization of Itaconic Acid

ABSTRACT Itaconic acid is an attractive biobased feedstock, presenting a bioderived alternative to common monomers such as acrylic acid. Its widespread adoption has been constricted by difficulties in its homopolymerization, which typically requires derivatization or extended reaction times to achieve significant monomer conversion. Here, we report the photoiniferter‐RAFT polymerization of itaconic acid, enabling improved monomer conversion and moderate control over dispersity. Kinetic parameters of homopolymerization are elucidated for a range of monomer concentrations, and the effects of irradiation on the photoiniferter are studied, with loss of end‐group fidelity observed over time. Despite this limitation, the resultant poly(itaconic acid)s have been demonstrated to undergo ω‐terminal labelling, and chain extension with another biosourced monomer, 2‐octyl acrylate, enabling the production of biobased building blocks for solution self‐assembly.