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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 . doi:10.1021/acs.macromol.0c01311 (In Press)
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WRAP-low-dispersity-polymers-ab-initio-emulsion-polymerization-improved-macroRAFT-agent-performance-heterogeneous-media-Perrier-2020.pdf - Accepted Version Embargoed item. Restricted access to Repository staff only until 3 September 2021. Contact author directly, specifying your specific needs. - Requires a PDF viewer. Download (1853Kb) |
Official URL: https://doi.org/10.1021/acs.macromol.0c01311
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 | ||||||
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| Subjects: | Q Science > QD Chemistry R Medicine > RS Pharmacy and materia medica |
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| 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: | 3 September 2020 | ||||||
| Dates: |
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| Date of first compliant deposit: | 11 September 2020 | ||||||
| DOI: | 10.1021/acs.macromol.0c01311 | ||||||
| Status: | Peer Reviewed | ||||||
| Publication Status: | In Press | ||||||
| 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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