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

Panagiotis Bexis; Jonathan T Husband; Haritz Sardon; Olivier Coulembier; Andrew P Dove

doi:10.1021/acs.macromol.3c02485

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

Macromolecules. 2024 Feb 28;57(5):2287-2294. doi: 10.1021/acs.macromol.3c02485. eCollection 2024 Mar 12.

Authors

Panagiotis Bexis¹, Jonathan T Husband¹, Haritz Sardon², Olivier Coulembier³, Andrew P Dove¹

Affiliations

¹ School of Chemistry, University of Birmingham, Edgbaston, Birmingham B15 2TT, U.K.
² POLYMAT, University of the Basque Country UPV/EHU, Joxe Mari Korta Center, Avda. Tolosa 72, 20018 Donostia-San Sebastian, Spain.
³ Center of Innovation and Research in Materials and Polymers (CIRMAP), Laboratory of Polymeric and Composite Materials, University of Mons, Mons B-7000, Belgium.

Abstract

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.