Organocatalytic Cationic Ring-Opening Polymerization of a Cyclic Hemiacetal Ester

We report the bulk cationic ring-opening polymerization of renewably sourced 2-methyl-1,3-dioxan-4-one (MDO) to yield a polyester with hydrolytically and thermally sensitive linkages that facilitate degradation. Neat monomer was successfully polymerized using a variety of protic acids as catalysts. We discovered that, with these catalysts, the cationic polymerization of MDO proceeds via two distinct mechanistic routes, namely, the activated...