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Investigating the influence of solvent quality on RAFT-mediated PISA of sulfonate-functional diblock copolymer nanoparticles

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Abstract

Polymerisation-induced self-assembly (PISA) has become widely recognised as a versatile and efficient strategy to prepare well-defined diblock copolymer nanoparticles in a range of solvents. In this article, we report the synthesis of anionic, sterically-stabilised, sulfonate-functional diblock copolymer nanoparticles via PISA using a reversible addition–fragmentation chain-transfer (RAFT) polymerisation formulation. Anionic poly(potassium 3-sulfopropyl methacrylate) (PKSPMA) macromolecular chain-transfer agents (macro-CTAs) were synthesised via RAFT solution polymerisation followed by chain-extension with benzyl methacrylate (BzMA) in alcohol/water mixtures to form PKSPMA–PBzMA nanoparticles. The influence of solvent quality on the formation of these nanoparticles was investigated by judiciously changing the alcohol/water ratio, the alcohol co-solvent (ethanol or methanol) and relative copolymer composition. The resulting diblock copolymer nanoparticles were analysed by dynamic light scattering (DLS), transmission electron microscopy (TEM), small-angle X-ray scattering (SAXS), and aqueous electrophoresis. The results demonstrated that nanoparticles with controllable diameters for a fixed copolymer composition can be prepared by altering the co-solvent composition. More specifically, when using different ratios of ethanol/water or methanol/water, the nanoparticle diameter can be tuned from approximately 20 to 200 nm with fixed copolymer composition. This indicates that the solvency of both the stabiliser and core-forming block has a marked impact on both the aggregation of polymer chains during self-assembly and the resulting nanoparticles. Additionally, these nanoparticles remain colloidally stable and highly anionic over a wide pH range from 4 to 10, as judged by aqueous electrophoresis.

Graphical abstract: Investigating the influence of solvent quality on RAFT-mediated PISA of sulfonate-functional diblock copolymer nanoparticles

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Supplementary files

Article information


Submitted
20 Dec 2019
Accepted
03 Feb 2020
First published
04 Feb 2020

Polym. Chem., 2020, Advance Article
Article type
Paper

Investigating the influence of solvent quality on RAFT-mediated PISA of sulfonate-functional diblock copolymer nanoparticles

S. Wen, J. G. Saunders and L. A. Fielding, Polym. Chem., 2020, Advance Article , DOI: 10.1039/C9PY01912J

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