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

Pengfei Zhang; Viko Ladelta; Nikos Hadjichristidis

doi:10.1021/jacs.3c03253

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

J Am Chem Soc. 2023 Jul 12;145(27):14756-14765. doi: 10.1021/jacs.3c03253. Epub 2023 Jun 29.

Authors

Pengfei Zhang¹, Viko Ladelta¹, Nikos Hadjichristidis¹

Affiliation

¹ Polymer Synthesis Laboratory, Chemistry Program, KAUST Catalysis Center, Physical Sciences and Engineering Division, King Abdullah University of Science and Technology (KAUST), Thuwal 23955, Saudi Arabia.

Abstract

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, M_n 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.