Well-Defined PDMAEA Stars via Cu(0)-Mediated Reversible Deactivation Radical Polymerization

Abstract

(2016) Well-defined PDMAEA stars via Cu(0)-mediated reversible deactivation radical polymerisation. Macromolecules, 49 (23). pp. 8914-8924. Permanent WRAP URL:http://wrap.warwick.ac.uk/83692 Copyright and reuse:The Warwick Research Archive Portal (WRAP) makes this work by researchers of the University of Warwick available open access under the following conditions. Copyright © and all moral rights to the version of the paper presented here belong to the individual author(s) and/or other copyright owners. To the extent reasonable and practicable the material made available in WRAP has been checked for eligibility before being made available.Copies of full items can be used for personal research or study, educational, or not-for profit purposes without prior permission or charge. Provided that the authors, title and full bibliographic details are credited, a hyperlink and/or URL is given for the original metadata page and the content is not changed in any way. Publisher's 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 http://pubs.acs.org/page/policy/articlesonrequest/index.html ." A note on versions:The version presented here may differ from the published version or, version of record, if you wish to cite this item you are advised to consult the publisher's version. Please see the 'permanent WRAP URL above for details on accessing the published version and note that access may require a subscription. AbstractThe 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.

The hydrolytic behavior of N,N′-(dimethylamino)ethyl acrylate-functionalized polymeric stars

“…reported that hydrolysis of a PDMAEA armed star, whose arms consisted of PDMAEA homopolymers, was found to undergo a similar rate of hydrolysis compared to those reported for both the linear homopolymers and graft copolymers, 38 and Perrier and co-workers reported the hydrolysis of P(dimethyl siloxaneb-DMAEA) block copolymers, which exhibited the same effect of quaternization on the prevention of PDMAEA hydrolysis as noted by Monteiro and co-workers. 39 Whilst the aforementioned studies indicate little effect of polymer structure on the hydrolysis behavior, hydrolysis of the PDMAEA occurs when the polymers are in a fully hydrated environment.…”

Tailoring polymer dispersity and shape of molecular weight distributions: methods and applications

“…[6][7][8] However, the discoveries of anionic 9 and cationic 10 polymerisation as well as controlled radical polymerisation methodologies including atom transfer radical polymerisation (ATRP), 11,12 reversible addition-fragmentation chain-transfer (RAFT) polymerisation 13 and nitroxide mediated polymerisation (NMP) 14 have enabled the synthesis of well-dened macromolecules with controlled molecular weight, architecture, end-group delity and dispersity. [15][16][17][18][19][20][21][22][23] In fact, the high end-group delity and the controlled nature of the polymerisation is typically conrmed by low dispersity values and as such dispersities in the range of Đ z 1.01-1.20 are routinely targeted. [24][25][26][27][28][29][30][31][32] Conversely, broader molecular weight distributions (Đ > 1.4) are oen considered to be a sign of uncontrolled or "failed" polymerisation and necessitate additional optimisation to reduce the dispersity.…”

Cu(0)-RDRP of styrene: balancing initiator efficiency and dispersity

“…The development of reversible addition fragmentation chain-transfer (RAFT) [1][2][3] polymerisation, nitroxide mediated polymerisation (NMP) [4][5][6] and atom transfer radical polymerisation (ATRP) [7][8][9][10][11] have allowed the synthesis of complex polymeric materials with controlled architecture and molecular weight, narrow molecular weight distributions and high end group functionality. [12][13][14][15][16][17][18][19][20] Among these techniques, Cu(0)-wire RDRP 21 (single electron transfer living radical polymerisation (SET LRP) 22 or supplemental activator and reducing agent (SARA) ATRP) 23 has attracted considerable attention as a versatile and robust methodology demonstrating broad monomer scope, yielding polymers with high end group fidelity even at near-quantitative conversions. 24,25 Perhaps the most significant advantage of Cu(0)-RDRP is its simplicity 26 as the reactions can often be carried out in a disposable vial (rather than Schlenk tubes) with simple deoxygenation via nitrogen bubbling for a few minutes being sufficient for a controlled polymerisation, rather than time-consuming freeze-pump-thaw cycles.…”