Terpenoid-based high-performance polyester with tacticity-independent crystallinity and chemical circularity

The development of chemically circular, bio-based polymers is an urgently needed solution to combat the plastic waste crisis. However, the most prominent, commercially implemented bio-based aliphatic polyester, poly(lactic acid) (PLA), is brittle, therefore largely limiting its broad applications. Herein, we introduce a class of aliphatic polyesters produced through the ring-opening polymerization (ROP) of (1R,5S)-8,8-dimethyl-3-oxabicyclo[3.2.1]octan-2-one (D-CamL) and the racemic mixture (rac-CamL), which exhibit superior material properties relative to PLA. A metal-based or organic catalyst was used for the modulation of polymer tacticity. Notably, regardless of tacticity, poly(CamL) exhibits intrinsic crystallinity, resulting in polyesters with high yield stress (24–39 MPa), high Young’s modulus (1.36–2.00 GPa), tunable fracture strains (6%–218%), and high melting temperatures (161°C–225°C). Importantly, poly(CamL) can be chemically recycled to monomer in high yield, and virgin-quality poly(CamL) is obtained after repolymerization. Overall, poly(CamL) represents a new class of bio-derived and chemically circular high-performance polyesters.