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Issue 1, 2021

Polymerization-induced self-assembly via RAFT in emulsion: effect of Z-group on the nucleation step

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Abstract

Polymerization-induced self-assembly (PISA) has emerged as one of the most powerful and widely employed techniques for preparation of block copolymer and polymeric nanoparticles in dispersed systems. Its success relies on a rapid, easily scalable and straightforward process, associated with the ability to readily control nanoparticle morphology. In the present work, we have investigated the effect of the Z-group of RAFT agents ZC([double bond, length as m-dash]S)–SR on the nucleation step of aqueous RAFT PISA performed in environmentally friendly emulsion polymerization. Seven different poly(acrylic acid) (PAA) and poly(methacrylic acid) (PMAA) macroRAFTs were synthesized using RAFT agents containing Z-groups of different hydrophilicity. Slow polymerizations and incomplete chain extension reactions were observed for systems with the most hydrophilic Z-group, while the more hydrophobic Z groups led to higher polymerization rates and very successful chain extensions. A mechanism based on Z-group induced RAFT exit is proposed to rationalize this surprising behaviour, providing important information on the mechanistic understanding and optimization of PISA in emulsion.

Graphical abstract: Polymerization-induced self-assembly via RAFT in emulsion: effect of Z-group on the nucleation step

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Article information


Submitted
13 Sep 2020
Accepted
16 Oct 2020
First published
16 Oct 2020

Polym. Chem., 2021,12, 122-133
Article type
Paper

Polymerization-induced self-assembly via RAFT in emulsion: effect of Z-group on the nucleation step

T. R. Guimarães, Y. L. Bong, S. W. Thompson, G. Moad, S. Perrier and P. B. Zetterlund, Polym. Chem., 2021, 12, 122 DOI: 10.1039/D0PY01311K

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