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

Ellis Hancox; Matthew J. Derry; Martin J. Greenall; Steven Huband; L Al-Shok; James S. Town; Paul D. Topham; David M. Haddleton

doi:10.1039/D2SC00720G

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

Ellis Hancox, Matthew J. Derry, Martin J. Greenall, Steven Huband, L Al-Shok, James S. Town, Paul D. Topham^*, David M. Haddleton^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

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.

Original language	English
Pages (from-to)	4019-4028
Number of pages	10
Journal	Chemical Science
Volume	13
Issue number	14
Early online date	14 Mar 2022
DOIs	https://doi.org/10.1039/D2SC00720G
Publication status	Published - 14 Mar 2022

Bibliographical note

© 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/.

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10.1039/D2SC00720GLicence: CC BY 3.0

Hancox Derry Topham Haddleton et al Heterotelechelic homopolymers
© 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/
Final published version, 0.99 MBLicence: CC BY 3.0

Cite this

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title = "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 ({\D} = 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.",

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AU - Topham, Paul D.

AU - Haddleton, David M.

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AB - 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.

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

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