Clean Polymerization Strategy for Recyclable Polydiene-Derivatives

Since the advent of polymer science, numerous polymerization methods have been developed, with most commercial polymers currently produced via gas-phase or solution-phase processes involving sophisticated initiators, catalysts, and additives. Here, we introduce a novel ultra-clean polymerization strategy for the controllable synthesis of high molecular weight polydienes, eliminating the need for solvents, catalysts, or initiators. Our method employs various irradiation methods to generate long-lived radicals in muconate derivatives that enable precise chain propagation with minimized termination. This approach also facilitates the straightforward synthesis of ABA tri-block copolymers and efficient random copolymerization. Significantly, due to the inherently weakened carbon-carbon bonds, these polymers and copolymers can be readily depolymerized to their monomeric forms with high yields, promoting efficient chemical recycling.