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

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Guimarães, Thiago R., Bong, Y. Loong, Thompson, Steven W., Moad, Graeme, Perrier, Sébastien and Zetterlund, Per B. (2021) Polymerization-induced self-assembly via RAFT in emulsion : effect of Z-group on the nucleation step. Polymer Chemistry, 12 (1). pp. 122-133. doi:10.1039/D0PY01311K ISSN 1759-9954.

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Official URL: http://dx.doi.org/10.1039/D0PY01311K

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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.

Item Type: Journal Article
Subjects: Q Science > QD Chemistry
Divisions: Faculty of Science, Engineering and Medicine > Science > Chemistry
Faculty of Science, Engineering and Medicine > Medicine > Warwick Medical School
Library of Congress Subject Headings (LCSH): Polymerization, Addition polymerization, Diblock copolymers -- Synthesis, Block copolymers, Nanoparticles -- Synthesis
Journal or Publication Title: Polymer Chemistry
Publisher: Royal Society of Chemistry
ISSN: 1759-9954
Official Date: 2021
Dates:
DateEvent
2021Published
16 October 2020Available
16 October 2020Accepted
Volume: 12
Number: 1
Page Range: pp. 122-133
DOI: 10.1039/D0PY01311K
Status: Peer Reviewed
Publication Status: Published
Access rights to Published version: Restricted or Subscription Access
Date of first compliant deposit: 23 April 2021
Date of first compliant Open Access: 16 October 2021

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