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Updated: Sep 22, 2025

Synthesis of Monodisperse Cylindrical Nanoparticles via Crystallization-driven Self-assembly of Biodegradable Block Copolymers
Published on: June 20, 2019
One-Pot Synthesis of Block Copolymers by Orthogonal Ring-Opening Polymerization and PET-RAFT Polymerization at
Changkui Fu1, Jiangtao Xu1, Mitchell Kokotovic1
1Centre for Advanced Macromolecular Design (CAMD) and Australian Centre for NanoMedicine (ACN), School of Chemical Engineering, University of New South Wales, Sydney, NSW 2052, Australia.
Abstract:
Well-defined poly(ε-caprolactone)-b-poly(methyl acrylate) (PCL-b-PMA) block copolymers were synthesized at ambient temperature by one-pot combination of diphenyl phosphate (DPP)-catalyzed ring-opening polymerization (ROP) and photoinduced electron/energy transfer-reversible addition-fragmentation chain transfer (PET-RAFT) polymerization. Full orthogonality of PET-RAFT polymerization and DPP-catalyzed ROP was confirmed by kinetic studies, which allowed facile synthesis of PCL-b-PMA block copolymers without a specific polymerization sequence. The resulting PCL-b-PMA block copolymers synthesized by either sequential or simultaneous ROP and PET-RAFT polymerization showed remarkably low molecular weight distributions (≤1.15), indicating that both ROP and PET-RAFT polymerizations proceeded in a controlled manner. In contrast to previous synthetic methods to prepare block copolymers, this facile one-pot method allows for rapid synthesis of block copolymers controlled via visible light.
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