Multiple-responsive shape memory polyacrylonitrile/graphene nanocomposites with rapid self-healing and recycling properties.

It still remains a great challenge to endow polymer materials with multiple superior material properties by precise molecular design. Herein, we report a Diels-Alder (DA) based crosslinked polyacrylonitrile/graphene nanocomposite (PAN-DA/GR), which has multiple-responsive properties of shape memory, self-healing, and reprocessing in addition to enhanced mechanical properties. The graphene sheets, which are well dispersed in the DA-based crosslinked PAN network, can act as intrinsic localized thermal sources by converting the absorbed external IR/microwave energies into heat, to trigger the glass transition for elasticity-based shape memory properties and retro-DA (rDA) reactions for healing. The incorporation of Diels-Alder bonds also gives the material solid state plasticity through topological network rearrangement, thus leading to versatile shape adaptability. Moreover, both regional shape control and targeted self-healing of the nanocomposites can be simply achieved by IR laser irradiation. Besides, the incorporation of a small amount of graphene can significantly improve the mechanical strength with respect to the DA-based crosslinked PAN. Both DSC and in situ variable temperature 13 C solid-state NMR experiments were used to monitor the reversible DA reactions.