Abstract
An attempt was made to study theoretically the conditions of occurrence of co-solvency phenomena for quasi-ternary components systems consisting of a multicomponent polymer dissolved in a binary solvent mixture. For this purpose, Kamide and Matsuda theory on spinodal curve (SC) and critical solution point (CSP) for the quasi-ternary systems [Polym. J., 18, 347 (1986)] was employed. The co-solvency occurs generally only when the total polymer volume fractions vp at two spinodal points (v1=0 and v2=0), vp(1) and vp(2) satisfy the following two inequalities concurrently: 0<vp(1)<1 and 0<vp(2)<1. (Here, v1 and v2 are the volume fractions of solvents 1 and 2.) SC, CSP, and the cloud point curve (CPC) were calculated for a wide range of three thermodynamic interaction parameters χ12, χ13, and χ23 (the suffixes 1 and 2 mean solvents 1 and 2, respectively, the suffix 3, the polymer). Co-solvency occurs generally in the cases when (1) original polymer has smaller weight-average degree of polymerization Xw0, (2) the polymer has the smaller ratio of Xw0 to the number-average degree of polymerization Xn0 (i.e., Xw0/Xn0), and (3) the initial polymer volume fraction vp0 is smaller than that of the critical concentration vpc. There exists a specific χ12 value yielding the most wide composition range of co-solvency of the system concerned (for example χ12=1.4 for Xw0=300). When χ12=0, no co-solvency occurs. For larger χ12 (but not larger than 2.0), smaller χ13, and smaller χ23, co-nonsolvency was theoretically predicted to occur and in this case the system has two Flory solvent compositions.
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Matsuda, S., Kamide, K. Phase Equilibria of Quasi-Ternary Systems Consisting of Multi-Component Polymers in a Binary Solvent Mixture VII. Co-Solvency. Polym J 19, 211–219 (1987). https://doi.org/10.1295/polymj.19.211
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DOI: https://doi.org/10.1295/polymj.19.211