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Low-dispersity polymers in ab initio emulsion polymerization : improved macroRAFT agent performance in heterogeneous media

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Richardson, Robert A. E., Guimarães, Thiago R., Khan, Murtaza, Moad, Graeme, Zetterlund, Per B. and Perrier, Sébastien (2020) Low-dispersity polymers in ab initio emulsion polymerization : improved macroRAFT agent performance in heterogeneous media. Macromolecules, 53 (18). pp. 7672-7683. doi:10.1021/acs.macromol.0c01311

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Official URL: https://doi.org/10.1021/acs.macromol.0c01311

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Abstract

We demonstrate that the in-built monomer-feeding mechanism in an emulsion polymerization can be used to dramatically increase control (providing low molar mass dispersity (Đ) ≤1.15) over polymerizations mediated by reversible addition–fragmentation chain transfer (RAFT) agents with relatively low transfer constants (Ctr). An amphiphilic RAFT agent [RSC(═S)Z], based on a hydrophilic methacrylic R-group [Ċ(CH3)2CO2-PEG] and a hydrophobic Z group with Ctr ≈ 2, was used to mediate the polymerization of a range of methacrylate monomers under both heterogeneous and homogeneous conditions. Consistent with the low Ctr, batch miniemulsion or solution polymerizations did not provide polymers with low Đ. The issue of a low Ctr is overcome in an emulsion polymerization when the [monomer]/[RAFT agent] ratio at the locus of polymerization is substantially lower than the overall ratio, due to the presence of a discrete monomer droplet phase. The proposed mechanism is supported by a theoretical model. As a demonstration of the increased level of control achievable, the system has been exploited to generate methacrylate multiblock copolymers.

Item Type: Journal Article
Subjects: Q Science > QD Chemistry
R Medicine > RS Pharmacy and materia medica
Divisions: Faculty of Science > Chemistry
Library of Congress Subject Headings (LCSH): Emulsion polymerization, Addition polymerization, Nanoparticles, Fragmentation reactions
Journal or Publication Title: Macromolecules
Publisher: American Chemical Society
ISSN: 0024-9297
Official Date: 22 September 2020
Dates:
DateEvent
22 September 2020Published
3 September 2020Available
3 September 2020Accepted
Volume: 53
Number: 18
Page Range: pp. 7672-7683
DOI: 10.1021/acs.macromol.0c01311
Status: Peer Reviewed
Publication Status: Published
Publisher Statement: This document is the Accepted Manuscript version of a Published Work that appeared in final form in Macromolecules, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see http://dx.doi.org/10.1021/acs.macromol.0c01311
Access rights to Published version: Restricted or Subscription Access

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