LAUSR

Commodity copolymers offer many useful applications, and their durability is critical in maintaining desired functions and retaining sustainability. These studies show that primarily alternating styrene/n-butyl acrylate [p(Sty/nBA)] copolymers self-heal without external intervention when monomer molar ratios are within the 45:55-53:47 range. This behavior is attributed to the favorable interchain interactions between aliphatic nBA side groups being sandwiched by aromatic rings forming ring-and-lock associations driven by pi-sigma-pi (π-σ-π) interactions. Guided by molecular dynamics (MD) simulations combined with spectroscopic and thermomechanical analysis, the ring-and-lock interchain van der Waals forces between π orbitals of aromatic rings and sigma components of aliphatic side groups are responsible for self-healing. Despite the frequent occurrence of these interactions in biological systems (proteins, nucleic acids, lipids, and polysaccharides), these largely unexplored weak and ubiquitous molecular forces between the soft acid aliphatic and soft base aromatic electrons may be valuable assets in the development of polymeric materials with sustainable properties.