Abstract
Liquid-liquid equilibrium phase relations in polymer mixtures are analysed in some detail with the aid of classic thermodynamical considerations. Polymolecularity in the constituents causes cloudpoint curves not to represent coexisting phases and their extrema not to be identifyable with critical points. Such features should be taken into account when molecular theories are compared with experimental data. Multiple phase separations can be brought about by polymolecularity as well as by a special dependence of the interaction function on concentration. Molecular origins of the latter may be: 1) different numbers of nearest neighbour contacts between the various repeat units, 2) mutual influence of the flexibility of the polymer chains, 3) non uniform segment density, 4) free volume. Statistical copolymers have the extra complication of a distribution of chemical composition. The latter enhances the tendency towards multiple phase equilibrium, chemical composition and chain length governing details sensitively. In addition, differences in size between the repeat units appear to be of primary importance. Experimental methods suitable for thermodynamic measurements on the highly viscous mixtures in hand are briefly reviewed.
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Koningsveld, R., Kleintjens, L.A. (1985). Liquid-Liquid Phase Equilibria in Polymer Blends. In: Walsh, D.J., Higgins, J.S., Maconnachie, A. (eds) Polymer Blends and Mixtures. NATO ASI Series, vol 89. Springer, Dordrecht. https://doi.org/10.1007/978-94-009-5101-3_6
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