TY - JOUR
T1 - Living/Controlled Anionic Polymerization of Glycolide in Fluoroalcohols: Toward Sustainable Bioplastics
AU - Zhang, Pengfei
AU - Ladelta, Viko
AU - Hadjichristidis, Nikos
N1 - KAUST 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.).
PY - 2023/6/29
Y1 - 2023/6/29
N2 - 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.
AB - 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.
UR - http://hdl.handle.net/10754/692769
UR - https://pubs.acs.org/doi/10.1021/jacs.3c03253
U2 - 10.1021/jacs.3c03253
DO - 10.1021/jacs.3c03253
M3 - Article
C2 - 37382584
SN - 0002-7863
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
ER -