Volume 114, Number 4, May 2016
|Number of page(s)||6|
|Section||Condensed Matter: Structural, Mechanical and Thermal Properties|
|Published online||15 June 2016|
A statistical theory of coil-to-globule-to-coil transition of a polymer chain in a mixture of good solvents
1 G.A. Krestov Institute of Solution Chemistry of the Russian Academy of Sciences - Ivanovo, Russia
2 National Research University Higher School of Economics, Department of Applied Mathematics - Moscow, Russia
3 Lomonosov Moscow State University, Department of Chemistry - Moscow, Russia
4 Institut für Nichtklassische Chemie e.V., Universitat Leipzig - Leipzig, Germany
5 Ivanovo State University - Ivanovo, Russia
Received: 24 March 2016
Accepted: 25 May 2016
We present an off-lattice statistical model of a single polymer chain in mixed-solvent media. Taking into account the polymer conformational entropy, renormalization of solvent composition near the polymer backbone, the universal intermolecular excluded-volume and van der Waals interactions within the self-consistent field theory, the reentrant coil-to-globule-to-coil transition (co-nonsolvency) has been described in this paper. For convenience we split the system volume in two parts: the volume occupied by the polymer chain and the volume of bulk solution. Considering the equilibrium between two sub-volumes, the polymer solvation free energy as a function of radius of gyration and co-solvent mole fraction within internal polymer volume has been obtained. Minimizing the free energy of solvation with respect to its arguments, we show two qulitatively different regimes of co-nonsolvency. Namely, at sufficiently high temperature the reentrant coil-to-globule-to-coil transition proceeds smoothly. On the contrary, when the temperature drops below a certain threshold value a coil-globule transition occurs in the regime of first-order phase transition, i.e., discontinuous changes of the radius of gyration and the local co-solvent mole fraction near the polymer backbone. We show that, when the collapse of the polymer chain takes place, the entropy and enthalpy contributions to the solvation free energy of the globule strongly grow. From the first principles of statistical thermodynamics we confirm earlier speculations based on the MD simulations results that the co-nonsolvency is the essentially enthalpic-entropic effect and is caused by enthalpy-entropy compensation. We show that the temperature dependences of the solution heat capacity change due to the solvation of the polymer chain are in qualitative agreement with the differential scanning calorimetry data for PNIPAM in aqueous methanol.
PACS: 61.25.hp – Polymer swelling, cross linking / 31.70.Dk – Environmental and solvent effects
© EPLA, 2016
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