Copper-mediated living radical polymerization (SET-LRP) of lipophilic monomers from multi-functional initiators: reducing star–star coupling at high molecular weights and high monomer conversions

Waldron, Christopher; Anastasaki, Athina; McHale, Ronan; Wilson, Paul; Li, Zai-Dong; Smith, T. N.; Haddleton, David M.

doi:10.1039/c3py01241g

Cited by 53 publications

(88 citation statements)

References 53 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…[1][2][3][4][5][6][7][8][9][10][11] Control over the molecular weight distribution (MWD) and the rate of polymerization for SET-LRP is controlled through a selfregulated process 2, 12 driven by the disproportionation of Cu(I) to Cu(II) and Cu(0) in polar protic and aprotic solvents, water and their corresponding mixtures. Ligands stabilize the Cu(II) complex and further drive the equilibrium towards disproportionation.…”

Section: Introductionmentioning

confidence: 99%

Quantitative end-group functionalization of PNIPAM from aqueous SET-LRP via in situ reduction of Cu(ii) with NaBH₄

et al. 2016

View full text Add to dashboard Cite

show abstract

Section: Introductionmentioning

confidence: 99%

Quantitative end-group functionalization of PNIPAM from aqueous SET-LRP via in situ reduction of Cu(ii) with NaBH₄

et al. 2016

View full text Add to dashboard Cite

show abstract

“…[53][54] Indeed, Cu(0)-mediated RDRP has already been employed to yield well-defined stars, 55 including the synthesis of stars homopolymers in a biphasic system, which was shown to suppress star-star coupling. 56 However, non-functional monomers have been employed (typically methyl acrylate) in all cases, thus limiting the applications of the resultant materials. 57 Herein, we present the Cu(0)-mediated RDRP in dimethyl sulfoxide (DMSO) and isopropanol (IPA) solvents at ambient temperature to afford the synthesis of well-defined 4 and 8 arm PDMAEA stars.…”

Section: Introductionmentioning

confidence: 99%

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

et al. 2016

Self Cite

View full text Add to dashboard Cite

(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.

show abstract

“…lauryl acrylate. 13,14 Copper (Cu) catalysed radical polymerisation is finding increased applications in industry as it can be used in a wide range of monomer/solvent systems as well as being more tolerant to the presence of impurities and oxygen. 15 Additionally, it has been shown that RAFT is highly adaptable and effective at polymerising a large range of monomer types in a wide range of solvents with superior control over molar mass and dispersity for a variety of molecular architectures.…”

Section: Introductionmentioning

confidence: 99%

Functionalisation of MWCNTs with poly(lauryl acrylate) polymerised by Cu(0)-mediated and RAFT methods

et al. 2016

Self Cite

View full text Add to dashboard Cite

Permanent WRAP URL:http://wrap.warwick.ac.uk/79040 Copyright and reuse:The Warwick Research Archive Portal (WRAP) makes this work of 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 statement:First published by Royal Society of Chemistry 2016 http://dx.doi.org/10.1039/C6PY00522E 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. Poly (

show abstract

Copper-mediated living radical polymerization (SET-LRP) of lipophilic monomers from multi-functional initiators: reducing star–star coupling at high molecular weights and high monomer conversions

Cited by 53 publications

References 53 publications

Quantitative end-group functionalization of PNIPAM from aqueous SET-LRP via in situ reduction of Cu(ii) with NaBH₄

Quantitative end-group functionalization of PNIPAM from aqueous SET-LRP via in situ reduction of Cu(ii) with NaBH₄

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

Functionalisation of MWCNTs with poly(lauryl acrylate) polymerised by Cu(0)-mediated and RAFT methods

Contact Info

Product

Resources

About

Copper-mediated living radical polymerization (SET-LRP) of lipophilic monomers from multi-functional initiators: reducing star–star coupling at high molecular weights and high monomer conversions

Cited by 53 publications

References 53 publications

Quantitative end-group functionalization of PNIPAM from aqueous SET-LRP via in situ reduction of Cu(ii) with NaBH4

Quantitative end-group functionalization of PNIPAM from aqueous SET-LRP via in situ reduction of Cu(ii) with NaBH4

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

Functionalisation of MWCNTs with poly(lauryl acrylate) polymerised by Cu(0)-mediated and RAFT methods

Contact Info

Product

Resources

About

Quantitative end-group functionalization of PNIPAM from aqueous SET-LRP via in situ reduction of Cu(ii) with NaBH₄

Quantitative end-group functionalization of PNIPAM from aqueous SET-LRP via in situ reduction of Cu(ii) with NaBH₄