Hancox, Ellis, Derry, Matthew J., Greenall, Martin J., Huband, Steven, Al-Shok, L, Town, James S., Topham, Paul D. and Haddleton, David M. (2022). Heterotelechelic homopolymers mimicking high χ – ultralow N block copolymers with sub-2 nm domain size. Chemical Science, 13 (14), pp. 4019-4028.
Abstract
Three fluorinated, hydrophobic initiators have been utilised for the synthesis of low molecular mass fluoro-poly(acrylic acid) heterotelechelic homopolymers to mimic high chi (χ)–low N diblock copolymers with ultrafine domains of sub-2 nm length scale. Polymers were obtained by a simple photoinduced copper(II)-mediated reversible-deactivation radical polymerisation (Cu-RDRP) affording low molecular mass (<3 kDa) and low dispersity (Đ = 1.04–1.21) homopolymers. Heating/cooling ramps were performed on bulk samples (ca. 250 μm thick) to obtain thermodynamically stable nanomorpologies of lamellar (LAM) or hexagonally packed cylinders (HEX), as deduced by small-angle X-ray scattering (SAXS). Construction of the experimental phase diagram alongside a detailed theoretical model demonstrated typical rod–coil block copolymer phase behaviour for these fluoro-poly(acrylic acid) homopolymers, where the fluorinated initiator-derived segment acts as a rod and the poly(acrylic acid) as a coil. This work reveals that these telechelic homopolymers mimic high χ-ultralow N diblock copolymers and enables reproducible targeting of nanomorphologies with incredibly small, tunable domain size.
Publication DOI: | https://doi.org/10.1039/D2SC00720G |
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Divisions: | College of Engineering & Physical Sciences > Aston Institute of Materials Research (AIMR) College of Engineering & Physical Sciences > School of Infrastructure and Sustainable Engineering > Chemical Engineering & Applied Chemistry College of Engineering & Physical Sciences College of Engineering & Physical Sciences > Aston Institute of Urban Technology and the Environment (ASTUTE) College of Engineering & Physical Sciences > Aston Polymer Research Group |
Additional Information: | © 2022 The Author(s). Published by the Royal Society of Chemistry. This article is licensed under a Creative Commons Attribution 3.0 Unported License https://creativecommons.org/licenses/by/3.0/ Data availability: Raw data including DSC, GPC, MALDI TOF MS, NMR and SAXS (including movies) is available to download at https://wrap.warwick.ac.uk/163791/. |
Uncontrolled Keywords: | General Chemistry |
Publication ISSN: | 2041-6539 |
Last Modified: | 30 Sep 2024 13:00 |
Date Deposited: | 21 Mar 2022 18:09 |
Full Text Link: | |
Related URLs: |
https://wrap.wa ... k.ac.uk/163791/
(Related URL) https://pubs.rs ... 2/SC/D2SC00720G (Publisher URL) http://www.scop ... tnerID=8YFLogxK (Scopus URL) |
PURE Output Type: | Article |
Published Date: | 2022-03-14 |
Published Online Date: | 2022-03-14 |
Accepted Date: | 2022-03-13 |
Authors: |
Hancox, Ellis
Derry, Matthew J. ( 0000-0001-5010-6725) Greenall, Martin J. Huband, Steven Al-Shok, L Town, James S. Topham, Paul D. ( 0000-0003-4152-6976) Haddleton, David M. |