Photo-Iniferter RAFT synthesis of versatile, non-alternating poly(acrylate-co-isocyanides)

Non-alternating poly(isocyanide-co-acrylate) copolymers enable access to novel polymer microstructures with versatile chemistry and allow for designed mechanical properties, an important facet of combatting the plastic waste crisis. While previous syntheses used cobalt-mediated radical polymerizations, the cobalt complex exhibits side reactivity, compli- cating control over polymerization. This work describes the application of an orthogonal, photocontrolled RAFT polymeri- zation to a range of isocyanides with excellent temporal control. Under solvent-free conditions, adding monomers with a standard chain transfer agent (CTA) results in the synthesis of copolymers that are then transformed into several novel mi- crostructures. Interestingly, we discover that the isocyanide units can undergo cyclization of the backbone resulting in an unexampled polyamide-like copolymer containing the pyrrolidone ring. Moreover, we generate polyacrylic acid-like copol- ymers with small amounts of ketone linkages through hydrolysis, enabling faster degradation rates for this class of polymer.