Stereocomplexed Functional and Statistical Poly(lactide-carbonate)s via a Simple Organocatalytic System

The stereocomplexation of polylactide (PLA) has been widely relied upon to develop degradable, sustainable materials with increased strength and improved material properties in comparison to stereopure PLA. However, forming functionalized copolymers of PLA while retaining high crystallinity remains elusive. Herein, the controlled ring-opening copolymerization (ROCOP) of lactide (LA) and functionalized cyclic carbonate monomers is undertaken. The produced polymers are shown to remain crystalline up to 25 mol % carbonate content and are efficiently stereocomplexed with homopolymer PLA and copolymers of opposite chirality. Polymers with alkene and alkyne pendent handles are shown to undergo efficient derivatization with thiol-ene click chemistry, which would allow both the covalent conjugation of therapeutic moieties and tuning of material properties.