Hydrogen Bonding in Supramolecular Polymer Networks: Glasses, Melts, and Elastomers

Abstract

Nature utilizes hydrogen bonding to guide the supramolecular assembly of lipids, proteins, and DNA, thereby imparting remarkable stimuli-responsiveness, structure-forming ability, and elasticity. Supramolecular polymers and networks containing reversibly associating groups are now synthetically accessible and offer diverse properties that are highly sensitive to temperature and other stimuli. This review examines how dynamic hydrogen bonding between functional macromers influences supramolecular network formation and physical properties. The emphasis is on condensed phases, including concentrated solutions, melts, and glasses. We discuss how microscopic factors such as the polymer architecture, backbone mobility, mesoscopic ordering, and aggregation or phase segregation of binding groups influence the supramolecular structure, phase behavior, and dynamics of these materials. This understanding is crucial to advance emerging technologies such as thermoplastic elastomers, shape-memory elastomers, and self-healing materials.