Photoinduced Iron-Catalyzed ATRP of Renewable Monomers in Low-Toxicity Solvents: A Greener Approach

[Image: see text] Producing polymers from renewable resources via more sustainable approaches has become increasingly important. Herein we present the polymerization of monomers obtained from biobased renewable resources, employing an environmentally friendly photoinduced iron-catalyzed atom transfer radical polymerization (ATRP) in low-toxicity solvents. We demonstrate that renewable monomers can be successfully polymerized into sustainable polymers with controlled molecular weights and narrow molar mass distributions (Đ as low as 1.17). This is in contrast to reversible addition–fragmentation chain-transfer (RAFT) polymerization, arguably the most commonly employed method to polymerize biobased monomers, which led to poorer molecular weight control and higher dispersities for these specific monomers (Đs ∼ 1.4). The versatility of our approach was further highlighted by the temporal control demonstrated through intermittent “on/off” cycles, controlled polymerizations of a variety of monomers and chain lengths, oxygen-tolerance, and high end-group fidelity exemplified by the synthesis of block copolymers. This work highlights photoinduced iron-catalyzed ATRP as a powerful tool for the synthesis of renewable polymers.