Cunningham, V.J., Ning, Y., Armes, S.P. orcid.org/0000-0002-8289-6351 et al. (1 more author) (2016) Poly(N-2-(methacryloyloxy)ethyl pyrrolidone)-poly(benzyl methacrylate) diblock copolymer nano-objects via RAFT alcoholic dispersion polymerisation in ethanol. Polymer, 106. pp. 189-199. ISSN 0032-3861
Abstract
N-2-(methacryloyloxy)ethyl pyrrolidone (NMEP) is a highly polar monomer that is much more readily copolymerised with methacrylic monomers than its structural analogue, N-vinyl pyrrolidone. The RAFT solution polymerisation of NMEP has been conducted in ethanol at 70 °C while varying the degree of polymerisation (DP) from 70 to 400. Reducing the CTA/initiator molar ratio from 10.0 to 3.0 when targeting PNMEP100 led to a three-fold rate enhancement and increased the final monomer conversion from 72% to 98%. Targeting DPs of 200 or greater led to lower monomer conversions. DMF GPC analysis of a series of PNMEPx homopolymers confirmed a linear increase in molecular weight with conversion and relatively low dispersities (Mw/Mn < 1.26). A PNMEP50 macro-CTA was chain-extended with benzyl methacrylate (BzMA) via RAFT alcoholic dispersion polymerisation. High BzMA conversions (>90%) were obtained and electron microscopy studies indicated that a range of diblock copolymer morphologies, e.g. spheres, worms and vesicles, were produced by polymerisation-induced self-assembly (PISA). Finally, a PNMEP47-PBzMA243 diblock copolymer was synthesised via a convenient 'one-pot' protocol whereby a PNMEP47 macro-CTA was first prepared at 97% conversion, followed by in situ RAFT dispersion polymerisation of BzMA to produce diblock copolymer nano-objects. TEM analysis of aliquots taken during the diblock copolymer synthesis indicated a gradual evolution in copolymer morphology from spherical micelles after 1 h to a pure vesicle phase after 8 h via intermediate mixed phases (including worms).
Metadata
Item Type: | Article |
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Authors/Creators: |
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Copyright, Publisher and Additional Information: | © 2016 Elsevier. This is an author produced version of a paper subsequently published in Polymer. Uploaded in accordance with the publisher's self-archiving policy. Article available under the terms of the CC-BY-NC-ND licence (https://creativecommons.org/licenses/by-nc-nd/4.0/) |
Keywords: | Block copolymer nanoparticles; Dispersion polymerisation; Polymerisation-induced self-assembly |
Dates: |
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Institution: | The University of Sheffield |
Academic Units: | The University of Sheffield > Faculty of Science (Sheffield) > Department of Chemistry (Sheffield) |
Funding Information: | Funder Grant number EUROPEAN RESEARCH COUNCIL PISA - 320372 ENGINEERING AND PHYSICAL SCIENCE RESEARCH COUNCIL (EPSRC) EP/I012060/1 |
Depositing User: | Symplectic Sheffield |
Date Deposited: | 21 Dec 2016 12:33 |
Last Modified: | 27 Jul 2017 16:26 |
Published Version: | https://doi.org/10.1016/j.polymer.2016.07.072 |
Status: | Published |
Publisher: | Elsevier |
Refereed: | Yes |
Identification Number: | 10.1016/j.polymer.2016.07.072 |
Open Archives Initiative ID (OAI ID): | oai:eprints.whiterose.ac.uk:109729 |
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Filename: PNMEP-PBzMA alcoholic dispersion polym Final.pdf
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