Hydrolyzable Graft Copolymers with In-Chain Esters from Polyethylene via Oxidative Chlorination

Hydrolyzable graft copolymers are high-value specialty polymers that can be chemically degraded under mild conditions, with diverse properties and applications stemming from the choice of main and grafted side-chains. Converting polyethylenes (PEs) into graft copolymers post-synthetically is thus an appealing valorization strategy, but existing methods leave the unreactive, difficult-to-degrade PE backbone intrinsically unchanged. Herein, we exploited oxidative chlorination as a versatile method to convert PEs into diverse hydrolyzable graft copolymers containing in-chain ester linkages. First, ester and chloro groups were simultaneously added to PE’s hydrocarbon backbone, where the latter allows different copolymers to be grafted on using commercially available vinyl monomers by ATRP. The resulting PE-graft-copolymers show tunable properties exemplified by varying surface wettability, and their in-chain ester linkages were hydrolyzable in refluxing basic aqueous conditions that are much milder than pyrolysis. Our approach offers new opportunities to valorize ubiquitous, low-cost PEs into diverse graft copolymers with enhanced intrinsic degradability for targeted applications.