Co-non-solvency: mean-field polymer theory does not describe polymer collapse transition in a mixture of two competing good solvents

The Journal of Chemical Physics
Debashish MukherjiKurt Kremer

Abstract

Smart polymers are a modern class of polymeric materials that often exhibit unpredictable behavior in mixtures of solvents. One such phenomenon is co-non-solvency. Co-non-solvency occurs when two (perfectly) miscible and competing good solvents, for a given polymer, are mixed together. As a result, the same polymer collapses into a compact globule within intermediate mixing ratios. More interestingly, polymer collapses when the solvent quality remains good and even gets increasingly better by the addition of the better cosolvent. This is a puzzling phenomenon that is driven by strong local concentration fluctuations. Because of the discrete particle based nature of the interactions, Flory-Huggins type mean field arguments become unsuitable. In this work, we extend the analysis of the co-non-solvency effect presented earlier [D. Mukherji et al., Nat. Commun. 5, 4882 (2014)]. We explain why co-non-solvency is a generic phenomenon, which can only be understood by the thermodynamic treatment of the competitive displacement of (co)solvent components. This competition can result in a polymer collapse upon improvement of the solvent quality. Specific chemical details are not required to understand these complex conformational transiti...Continue Reading

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Citations

Dec 1, 2015·The Journal of Physical Chemistry. B·Francisco Rodriguez-RoperoNico F A van der Vegt
Oct 10, 2015·The Journal of Chemical Physics·Jacek DudowiczJack F Douglas
Jan 18, 2017·The Journal of Physical Chemistry. B·Halil I OkurPavel Jungwirth
Sep 19, 2015·Soft Matter·Tiago E de OliveiraKurt Kremer
Nov 9, 2017·Soft Matter·Yu A Budkov, A L Kolesnikov
Oct 11, 2016·Physical Chemistry Chemical Physics : PCCP·Andrea Pica, Giuseppe Graziano
Dec 23, 2017·Journal of Physics. Condensed Matter : an Institute of Physics Journal·Yu A Budkov, M G Kiselev
Nov 23, 2017·Journal of Physics. Condensed Matter : an Institute of Physics Journal·Debashish MukherjiKurt Kremer
Feb 28, 2018·Physical Chemistry Chemical Physics : PCCP·Andrea Pica, Giuseppe Graziano
Nov 11, 2017·Nature Communications·Debashish MukherjiKurt Kremer
Sep 21, 2017·Langmuir : the ACS Journal of Surfaces and Colloids·Xueqian ChenHonglai Liu
Feb 15, 2018·The Journal of Physical Chemistry. B·Divya Nayar, Nico F A van der Vegt

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