Prediction of polymer mixture compatibility by Monte Carlo simulation of intermolecular binary interactions

We have evaluated conformational and orientational averages of binary interaction integrals for pairs of chains constituting atomistic representations of short polymer molecules. By considering A–A, B–B and A–B pairs, we relate these results with the Flory–Huggins parameter for the A–B mixtures. This parameter is commonly accepted as a good indicator of compatibility. Since the method ignores the simultaneous interactions with other molecules in the mixture, the local environment is approximately described by introducing an effective medium dielectric constant whose value is conveniently parameterized. The results for four different real systems are compared with data obtained from experimental neutron scattering data. The method qualitatively predicts the sign and variation with temperature in the four different cases, also showing a reasonable quantitative agreement in some of the cases. Its performance is discussed in comparison with a standard method that evaluates the Flory–Huggins parameter by calculating an average of the intermolecular energy of two molecules in contact, taking also into account their off-lattice Flory–Huggins coordination numbers.