Competing Dipolar and van der Waals Forces in Dynamic Self‐Healing of Poly(Ionic Liquid) Copolymers

Abstract These studies elucidate the origin of molecular processes involved in the self‐healing of imidazolium‐based poly(ionic liquid) copolymers (PILCs) subjected to dynamic surface oscillating forces (SOF). In contrast to their counterpart homopolymers, which are either brittle or exhibit irreversible responses, PILCs composed of short (‐CH 3 ; Me) and long (–CH) 2 ) 3 CH 3 ; Bu) aliphatic side chains attached to the cation‐anion pair composed of a 50/50 monomer molar ratio (poly(Me/Bu 50/50)) exhibit remarkable recovery. These dynamic responses arise from the competing polar and dipolar forces attributed to a balanced coexistence of ordered and disordered states involving the reversible rearrangements of H‐bonding, ionic interactions, and London dispersion forces. These copolymer composition‐driven processes exhibit dynamic recovery due to significant entropy increases, causing energy dissipation and reversible segmental rearrangements to achieve energetically favorable states. Spectroscopic FT‐IR measurements combined with 2D correlation spectroscopic (2D‐COS) analysis supported by molecular dynamics (MD) simulations reveal the significance of short‐ and long‐forces involved in polar‐dipolar interactions that enable dynamic recovery. The combination of directional and non‐directional entropy‐driven interchanges appears promising for identifying PILC architectures capable of mechanical adaptability, dynamic self‐healing, and ionic conductivity.