Solvent selectivity governs the emergence of temperature responsiveness in block copolymer self-assembly

Alessandro Ianiro (Corresponding author), Marco M.R.M. Hendrix, Paul Joshua Hurst, Joseph P. Patterson, Mark Vis, Michael Sztucki, A. Catarina C. Esteves, Remco Tuinier

Onderzoeksoutput: Bijdrage aan tijdschriftTijdschriftartikelAcademicpeer review


In highly selective solvents, block copolymers (BCPs) form association colloids, while in solvents with poor selectivity, they exhibit a temperature-controlled (de)mixing behavior. Herein, it is shown that a temperature-responsive self-assembly behavior emerges in solvent mixtures of intermediate selectivity. A biocompatible poly-ethylene(oxide)-block-poly-ϵ-caprolactone (PEO-PCL) BCP is used as a model system. The polymer is dissolved in solvent mixtures containing water (a strongly selective solvent for PEO) and ethanol (a poorly selective solvent for PEO) to tune the solvency conditions. Using synchrotron X-ray scattering, cryogenic transmission electron microscopy, and scanning probe microscopy, it is shown that a rich temperature-responsive behavior can be achieved in certain solvent mixtures. Crystallization of the PCL block enriches the phase behavior of the BCP by promoting sphere-to-cylinder morphology transitions at low temperatures. Increasing the water fraction in the solvent causes a suppression of the sphere-to-cylinder morphology transition. These results open up the possibility to induce temperature-responsive properties on demand in a wide range of BCP systems.

Originele taal-2Engels
Pagina's (van-tot)2912-2920
Aantal pagina's9
Nummer van het tijdschrift6
StatusGepubliceerd - 4 mrt. 2021

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© XXXX 2021 The Authors. Published by American Chemical Society.

Copyright 2021 Elsevier B.V., All rights reserved.


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