Heterotelechelic homopolymers mimicking high χ – ultralow N block copolymers with sub-2 nm domain size

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
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: Chemistry(all)
Publication ISSN: 2041-6539
Last Modified: 17 Jun 2024 08:02
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. (ORCID Profile 0000-0001-5010-6725)
Greenall, Martin J.
Huband, Steven
Al-Shok, L
Town, James S.
Topham, Paul D. (ORCID Profile 0000-0003-4152-6976)
Haddleton, David M.

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