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

Hancox, E., Derry, M. J., Greenall, M. J. , Huband, S., Al-Shok, L., Town, J. S., Topham, P. D. and Haddleton, D. M. (2022) Heterotelechelic homopolymers mimicking high chi – ultralow N block copolymers with sub-2 nm domain size. Chemical Science, 13 . pp. 4019-4028. ISSN 2041-6520

Full content URL: https://doi.org/10.1039/D2SC00720G

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Heterotelechelic homopolymers mimicking high chi – ultralow N block copolymers with sub-2 nm domain size
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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−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 chi-ultralow N diblock copolymers and enables reproducible targeting of nanomorphologies with incredibly small, tunable domain size.

Keywords:polymers, Self-assembly
Subjects:F Physical Sciences > F300 Physics
F Physical Sciences > F162 Polymer Chemistry
F Physical Sciences > F100 Chemistry
Divisions:College of Science > School of Mathematics and Physics
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ID Code:48916
Deposited On:11 Apr 2022 12:51

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