Phase behavior predictions for polymer blends containing reversibly associating endgroups

A mean field model is developed to predict how polymer-polymer miscibility changes if polymers are functionalized with noncovalent, reversibly binding endgroups. The free-energy model is based on the Flory-Huggins mixing theory and has been modified using Painter's association model to account for equilibrium self-association of endgroups. Model input parameters include the length of polymer chains, a temperature-dependent interaction parameter, and a temperature-dependent equilibrium constant for each type of associating endgroup. The analysis is applied to 12 possible blend combinations involving self-complementary interactions and seven combinations involving hetero-complementary [i.e. donor-acceptor (DA)] interactions. Combinations involve both monofunctional and telechelic associating chains. Predicted phase diagrams illustrate how self-complementary interactions can stabilize two-phase regions and how DA interactions can stabilize single phase regions. The model is a useful tool in understanding the delicate balance between the combinatorial entropy of mixing polymer chains, the repulsive interactions between dissimilar polymers, and the additional enthalpic and entropic changes due to endgroup association of chain ends. (c) 2007 Wiley Periodicals, Inc.