100th Anniversary of Macromolecular Science Viewpoint: The Role of Hydrophobicity in Polymer Phenomena

The seemingly simple notion of the hydrophobic effect can be viewed from multiple angles involving theory, simulation, and experiments. This viewpoint examines five attributes of predictive models to enhance synthetic efforts as well as experimental methods to quantify hydrophobicity. In addition, we compare existing predictive models against experimental data for polymer surface tension, lower critical solution temperature, solution self-assembly morphology, and degradation behavior. Key conclusions suggest that both the Hildebrand solubility parameters (HSPs) and surface area-normalized Log P (Log P SA^-1) values provide unique and complementary insights into polymer phenomena. In particular, HSPs appear to better describe bulk polymer phenomena for thermoplastics such as surface tension, while Log P SA^-1 values are well-suited for describing and predicting the behavior of polymers in solution.