Water accelerated self-healing of hydrophobic copolymers

Previous studies have shown that copolymer compositions can significantly impact self-healing properties. This was accomplished by enhancement of van der Waals (vdW) forces which facilitate self-healing in relatively narrow copolymer compositional range. In this work we report the acceleration of self-healing in alternating/random hydrophobic acrylic-based copolymers in the presence of confined water molecules. Under these conditions competing vdW interactions do not allow H2O-diester H-bonding, thus forcing nBA side groups to adapt L-shape conformations, generating stronger dipole-dipole interactions resulting in shorter inter-chain distances compared to 'key-and-lock' associations without water. The perturbation of vdW forces upon mechanical damage in the presence of controllable amount of confined water is energetically unfavorable leading the enhancement of self-healing efficiency of hydrophobic copolymers by a factor of three. The concept may be applicable to other self-healing mechanisms involving reversible covalent bonding, supramolecular chemistry, or polymers with phase-separated morphologies. Self-healing of polymers became a vivid research area, but self-healing under water and its mechanistic concepts are less investigated. Here, the authors report water accelerated self-healing in a pMMA/nBA copolymer and demonstrate that perturbation of ubiquitous van der Walls forces upon mechanical damage in hydrophobic polymers in the presence of water is energetically unfavorable and accelerates self-healing.