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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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WRAP-polymerization-induced-self-assembly-via-RAFT-emulsion-effect-Z-group-nucleation-step-Perrier-2021 .pdf - Accepted Version - Requires a PDF viewer. Download (2539Kb) | Preview |
Official URL: http://dx.doi.org/10.1039/D0PY01311K
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 | ||||||||
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| Subjects: | Q Science > QD Chemistry | ||||||||
| Divisions: | Faculty of Science, Engineering and Medicine > Science > Chemistry Faculty of Science, Engineering and Medicine > Medicine > Warwick Medical School |
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| 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: |
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| 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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