Living/Controlled Anionic Polymerization of Glycolide in Fluoroalcohols: Toward Sustainable Bioplastics

Ring-opening polymerization(ROP) is a promising approachto accessingwell-defined polyesters with superior (bio)degradability and recyclability.However, the living/controlled polymerization of glycolide (GL), awell-known sustainable monomer derived from carbon monoxide/dioxide,has never been reported due to the extremely low solubility of itspolymer in common solvents. Herein, we report the first living/controlledanionic ROP of GL in strong protic fluoroalcohols (FAs), which areconventionally considered incompatible with anionic polymerization.Well-defined polyglycolide (PGA, D < 1.15, M (n) up to 55.4 kg mol(-1)) andvarious PGA-based macromolecules are obtained at room temperaturefor the first time. NMR titration and computational studies revealedthat FAs simultaneously activate the chain end and monomer withoutbeing involved in initiation. Low-boiling-point FAs and PGA can berecycled through simple distillation and sublimation at 220 & DEG;Cin vacuo, respectively, providing a promising sustainable alternativefor tackling plastic pollution problems.

Automated summary

This study reports the successful living/controlled anionic ring-opening polymerization of glycolide in strong protic fluoroalcohols, which are conventionally considered incompatible with anionic polymerization. Well-defined polyglycolide and various PGA-based macromolecules were obtained for the first time at room temperature. The low-boiling-point fluoroalcohols and polyglycolide can be recycled through simple distillation and sublimation, providing a promising sustainable alternative for tackling plastic pollution problems.