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Well-defined PDMAEA stars via Cu(0)-mediated reversible deactivation radical polymerisation

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Whitfield, Richard, Anastaskia, Athina, Truong, Nghia P., Wilson, Paul, Kempe, Kristian, Burns, James A., Davis, Thomas P. and Haddleton, David M. (2016) Well-defined PDMAEA stars via Cu(0)-mediated reversible deactivation radical polymerisation. Macromolecules, 49 (23). pp. 8914-8924. doi:10.1021/acs.macromol.6b01511 ISSN 0024-9297 .

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Official URL: http://doi.org/10.1021/acs.macromol.6b01511

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Abstract

The Cu(0)-mediated reversible deactivation radical polymerisation of N,N’-dimethylaminoethyl acrylate in DMSO and IPA at ambient temperature using Cu(0) wire is investigated. Tetra-functional and octa-functional initiators were utilised to facilitate the synthesis of well-defined PDMAEA star homo and block copolymers with a range of molecular weights (Mn ~ 5000-41000 g mol-1). Both solvents demonstrated to be excellent media for the controlled polymerisation of DMAEA yielding narrow molecular weight distributions (Ð ~ 1.1) when the reactions were ceased at ~ 40% conversion. Interestingly, at high conversions (typically > 55%) high and low molecular weight shoulders were evident by SEC when DMSO and IPA were used respectively, suggesting large extent of termination and/or side reactions at prolonged reaction times. Nevertheless, high end group fidelity could be maintained when immediate precipitation of the polymers (at lower conversion) was performed yielding low dispersed P(DMAEA-b-MA) star block copolymers (Ð < 1.19, Mn ~ 20000 g mol-1). Importantly, guidelines on how to prevent hydrolysis, termination and side reactions of PDMAEA as well as how to purify and store such materials are also provided and discussed.

Item Type: Journal Article
Subjects: Q Science > QD Chemistry
Divisions: Faculty of Science, Engineering and Medicine > Science > Chemistry
Library of Congress Subject Headings (LCSH): Dimethylaminoethanol, Acrylates, Addition polymerization
Journal or Publication Title: Macromolecules
Publisher: American Chemical Society
ISSN: 0024-9297
Official Date: 13 December 2016
Dates:
DateEvent
13 December 2016Published
15 November 2016Available
7 October 2016Accepted
Volume: 49
Number: 23
Page Range: pp. 8914-8924
DOI: 10.1021/acs.macromol.6b01511
Status: Peer Reviewed
Publication Status: Published
Access rights to Published version: Restricted or Subscription Access
Date of first compliant deposit: 9 November 2016
Date of first compliant Open Access: 15 November 2017
Funder: University of Warwick, Australian Research Council (ARC), Syngenta UK (Firm), Advantage West Midlands (AWM), European Regional Development Fund (ERDF), Royal Society (Great Britain). Wolfson Research Merit Award (RSWRMA)
Grant number: Project number CE140100036 (ARC)

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