A ring to rule them all: a cyclic ketene acetal comonomer controls the nitroxide-mediated polymerization of methacrylates and confers tunable degradability.

2-Methylene-4-phenyl-1,3-dioxolane (MPDL) was successfully used as a controlling comonomer in NMP with oligo(ethylene glycol) methyl ether methacrylate (MeOEGMA) to prepare well-defined and degradable PEG-based P(MeOEGMA-co-MPDL) copolymers. The level of ester group incorporation is controlled, leading to reductions in molecular weight of up to 95% on hydrolysis. Neither the polymer nor its degradation products displayed cytoxicity. The method was also successfully applied to methyl methacrylate.