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

Jeffrey C Foster,Amanda K Pearce,Robert T Mathers,Rachel K O'Reilly,Irem Akar,Marcus C Grocott

doi:10.1021/acsmacrolett.0c00645

Jeffrey C Foster, Amanda K Pearce + Show 4 more

Open Access

https://doi.org/10.1021/acsmacrolett.0c00645

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Abstract

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.

Highlights

The seemingly simple notion of the hydrophobic effect can be viewed from multiple angles involving theory, simulation, and experiments
In the past few decades, many synthetic efforts have been directed toward understanding the relationships between molecular weight (MW) or molecular weight distribution (MWD) and polymer behaviors such as mechanical properties, solubility, stimuli-responsiveness, selfassembly, degradation behavior, or biological activity.[1,2]
We explore the influence of hydrophobicity on polymer solution behavior and, in particular, its role in (1) polymer surface energy; (2) polymer thermal transitions; (3) block copolymer self-assembly; and (4) polymer degradation via hydrolysis

Summary

Introduction

The seemingly simple notion of the hydrophobic effect can be viewed from multiple angles involving theory, simulation, and experiments. Hildebrand and Hansen solubility parameters and partition coefficients (Log P values) have been successfully exploited to predict solution behavior of small molecules, it is a complicated transition from small molecules, many of which have rigid polycyclic structures, to large flexible macromolecules.[4] despite their limitations, studies have shown that these parameters have promise for solving scientific challenges.[5−10]. In this Viewpoint, we aim to examine definitions of polymer hydrophobicity and highlight important features of predictive models.

Objectives

Conclusion