Self-Healing and Recyclable Hydrogels Reinforced with in Situ-Formed Organic Nanofibrils Exhibit Simultaneously Enhanced Mechanical Strength and Stretchability

In this work, self-healing and recyclable polymer hydrogels with simultaneously enhanced mechanical strength and stretchability are fabricated through the complexation of poly(acrylic acid) (PAA) with complexes of branched poly(ethylenimine) and 1-pyrenybutyric acid (PEI-PYA) to generate PAA/PEI-PYA complexes, which are further molded, dried, and rehydrated. The in situ-formed PYA nanofibrils with aggregated structures during the complexation process enable the simultaneous enhancement of the tensile strength and stretchability of the PAA/PEI-PYA hydrogels. The PAA/PEI-PYA hydrogels have a tensile strength of 1.13 ± 0.04 MPa and stretchability of 2970 ± 154%, which are 2.2 and 2.1 times higher than those of the PAA/PEI hydrogels. Meanwhile, the damaged PAA/PEI-PYA hydrogels can be efficiently healed or recycled at room temperature to regain their original mechanical strength and integrity because the dynamic nature of hydrogen-bonding and electrostatic interactions among PAA, PEI, and PYA endows the hydrogels with excellent healing and recycling capacity. This strategy of using aggregated nanofibrils to simultaneously enhance the tensile strength and stretchability of hydrogels can be extended to PAA/PEI hydrogels reinforced with aggregated nanofibrils of 9-anthracenecarboxylic acid and N,N′-di(propanoic acid)-perylene-3,4,9,10-tetracarboxylic diimide, demonstrating its generality for fabricating hydrogels with enhanced mechanical properties.