Ring-opening polymerization (ROP) is a promising approach to accessing well-defined polyesters with superior (bio)degradability and recyclability. However, the living/controlled polymerization of glycolide (GL), a well-known sustainable monomer derived from carbon monoxide/dioxide, has never been reported due to the extremely low solubility of its polymer in common solvents. Herein, we report the first living/controlled anionic ROP of GL in strong protic fluoroalcohols (FAs), which are conventionally considered incompatible with anionic polymerization. Well-defined polyglycolide (PGA, Đ < 1.15, Mn up to 55.4 kg mol–1) and various PGA-based macromolecules are obtained at room temperature for the first time. NMR titration and computational studies revealed that FAs simultaneously activate the chain end and monomer without being involved in initiation. Low-boiling-point FAs and PGA can be recycled through simple distillation and sublimation at 220 °C in vacuo, respectively, providing a promising sustainable alternative for tackling plastic pollution problems.
Bibliographical noteKAUST Repository Item: Exported on 2023-07-04
Acknowledgements: King Abdullah University of Science and Technology (KAUST) baseline funding is gratefully acknowledged. KAUST Supercomputing Laboratory (KSL) is acknowledged for computing resources. Prof. Alejandro J. Müller from University of the Basque Country UPV/EHU and Dr. Jiaxi Xu from KAUST are also acknowledged for their helpful discussions. This paper is dedicated to the memory of the late Professor Lew Fetters, a Titan of Polymer Science. Lew was an inspiring mentor and friend (N.H.).
ASJC Scopus subject areas
- Colloid and Surface Chemistry