Terpenoid-Based High-Performance Polyester with Tacticity-Independent Crystallinity and Chemical Circularity

Chem. 2024 Oct 10;10(10):3040-3054. doi: 10.1016/j.chempr.2024.05.024. Epub 2024 Jun 26.

Abstract

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 materials 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 (161-225 °C). Importantly, poly(CamL) can be chemically recycled to monomer in high yield and the virgin-quality poly(CamL) was obtained after repolymerization. Overall, poly(CamL) represents a new class of bio-derived and chemically circular high-performance polyesters.