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RAFT emulsion polymerization for (multi)block copolymer synthesis : overcoming the constraints of monomer order
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Khan, Murtaza, Guimarães, Thiago R., Choong, Kenneth, Moad, Graeme, Perrier, Sébastien and Zetterlund, Per B. (2021) RAFT emulsion polymerization for (multi)block copolymer synthesis : overcoming the constraints of monomer order. Macromolecules, 54 (2). pp. 736-746. doi:10.1021/acs.macromol.0c02415 ISSN 0024-9297 .
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WRAP-RAFT-emulsion-polymerization-(multi)block-copolymer-synthesis-overcoming-constraints-monomer-order-Perrier-2021.pdf - Accepted Version - Requires a PDF viewer. Download (2338Kb) | Preview |
Official URL: http://dx.doi.org/10.1021/acs.macromol.0c02415
Abstract
Synthesis of (multi)block copolymers using reversible addition–fragmentation chain transfer (RAFT) polymerization generally suffers from the limitation that the order of the blocks must be considered. Herein, syntheses of block copolymers by RAFT polymerization using trithiocarbonate RAFT species are conducted as solution, miniemulsion, and emulsion polymerizations to demonstrate that the issue of monomer order for styrene and butyl methacrylate can be largely overcome in emulsion polymerization under carefully chosen conditions. The presence of monomer droplets in emulsion polymerization—in addition to polymer particles that constitute the locus of polymerization—leads to a reduction in the ratio of RAFT end groups to monomer at the locus of polymerization. Consequently, fragmentation of the RAFT adduct radical in the “backward” (“wrong”) direction is associated with fewer monomer additions, thus minimizing the impact of this undesired kinetic event. It is demonstrated that RAFT emulsion polymerization can be exploited to prepare an alternating pentablock copolymer composed of methacrylates (with 10 mol % styrene) and styrene without consideration of monomer order, thereby significantly broadening the scope of RAFT polymerization for multiblock copolymer synthesis.
| 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 |
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| Library of Congress Subject Headings (LCSH): | Polymerization, Addition polymerization, Block copolymers -- Synthesis | ||||||||
| Journal or Publication Title: | Macromolecules | ||||||||
| Publisher: | American Chemical Society | ||||||||
| ISSN: | 0024-9297 | ||||||||
| Official Date: | 26 January 2021 | ||||||||
| Dates: |
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| Volume: | 54 | ||||||||
| Number: | 2 | ||||||||
| Page Range: | pp. 736-746 | ||||||||
| DOI: | 10.1021/acs.macromol.0c02415 | ||||||||
| Status: | Peer Reviewed | ||||||||
| Publication Status: | Published | ||||||||
| Reuse Statement (publisher, data, author rights): | 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.0c02415 | ||||||||
| Access rights to Published version: | Restricted or Subscription Access | ||||||||
| Date of first compliant deposit: | 23 April 2021 | ||||||||
| Date of first compliant Open Access: | 5 January 2022 |
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