Strong and Ultra‐tough Ionic Hydrogel Based on Hyperbranched Macro‐Cross‐linker: Influence of Topological Structure on Properties

The application of hydrogels often suffers from their inherent limitation of poor mechanical properties. Here, a carboxyl-functionalized and acryloyl-terminated hyperbranched polycaprolactone (PCL) was synthesized and used as a macro-cross-linker to fabricate a super strong and ultra-tough ionic hydrogel. The terminal acryloyl groups of hyperbranched PCL are chemically incorporated into the network to form covalent cross-links, which contribute to robust networks. Meanwhile, the hydrophobic domains formed by the spontaneous aggregation of PCL chains and coordination bonds between Fe³⁺ and COO^- groups serve as dynamic non-covalent cross-links, which enhance the energy dissipation ability. Especially, the influence of the hyperbranched topological structure of PCL on hydrogel properties has been well investigated, exhibiting superior strengthening and toughening effects compared to the linear one. Moreover, the hyperbranched PCL cross-linker also endowed the ionic hydrogel with higher sensitivity than the linear one when used as a strain sensor. As a result, this well-designed ionic hydrogel possesses high mechanical strength, superior toughness, and well ionic conductivity, exhibiting potential applications in the field of flexible strain sensors.