Radical Ring Opening Polymerization of Cyclic Ketene Acetals Derived From d-Glucal

[Image: see text] A cyclic ketene acetal (CKA) derived from d-glucal was synthesized, and its polymerization using free radicals has been investigated. NMR analysis of the resulting polymers revealed the formation of polyacetal–polyester copolymers, with up to 78% of ester linkages formed by radical ring-opening polymerization (rROP). Conversely, the polymerization of the monomer-saturated analogue only produced acetal linkages, demonstrating that the alkene functionality within the d-glucal pyranose ring is essential to promote ring-opening and ester formation, likely via the stabilization of an allyl radical. The thermal properties of the polymers were linked to the ratio of the ester and acetal linkages. Copolymerization with methyl methacrylate (MMA) afforded statistically PMMA-rich copolymers (66–98%) with linkages prone to hydrolytic degradation and decreased glass-transition temperatures. The retention of the pseudoglucal alkene function offers opportunities to functionalize further these bioderived (co)polymers.