Organocatalytic ring-opening polymerization of thionolactones: anything O can do, S can do better

Abstract

The H-bond mediated organocatalytic ring-opening polymerizations (ROPs) of four new thionolactone monomers are discussed. The kinetic and thermodynamic behavior of the ROPs is considered in the context of the parent lactone monomers. Organocatalysts facilitate the retention of the S/O substitution as well as the synthesis of copolymers. The thionoester moieties in the polymer backbone serve as a chemical handle for a facile crosslinking reaction, and the porosity of the resulting crosslinked polymer can be tuned by altering the thioester density in the (co)polymer. The crosslinked polymers are shown to be degradable in water, and an Au³⁺ recovery application is demonstrated.