Theory of glassy dynamics in conformationally anisotropic polymer systems

A mode coupling theory for the ideal glass transition temperature, or crossover temperature to highly activated dynamics in the deeply supercooled regime, T(c), has been developed for anisotropic polymer liquids. A generalization of a simplified mode coupling approach at the coarse-grained segment level is employed which utilizes structural and thermodynamic information from the anisotropic polymer reference interaction site model theory. Conformational alignment or/and coil deformation modifies equilibrium properties and constraining interchain forces thereby inducing anisotropic segmental dynamics. For liquid-crystalline polymers a small suppression of T(c) with increasing nematic or discotic orientational order is predicted. The underlying mechanism is reduction of the degree of coil interpenetration and intermolecular repulsive contacts due to segmental alignment. For rubber networks chain deformation results in an enhanced bulk modulus and a modest elevation of T(c) is predicted. The theory can also be qualitatively applied to systems that undergo nonuniversal local deformation and alignment, such as polymer thin films and grafted brush layers, and large elevations or depressions of T(c) are possible. Extension to treat directionally dependent collective barrier formation and activated hopping is possible.