Inorganic Ionic Polymerization‐Anchored Polymer Networks for Ultrastrong and Ultratough Eutectogels

ABSTRACT Eutectogels hold considerable promise for applications in flexible electronics, soft robotics, and protective systems owing to their combination of the environmental stability of deep eutectic solvents and the mechanical robustness of polymer networks. However, predominantly weak intermolecular interactions among polymer chains within eutectogels restrict their mechanical performance, making it challenging to simultaneously achieve high strength and high toughness. Herein, we propose an inorganic ionic polymerization‐anchored polymer network (IIP‐APN) strategy to construct ultrastrong and ultratough eutectogels. Specifically, calcium phosphate oligomers (CPO) are incorporated into the polyvinyl alcohol (PVA) chain network to serve as nanoanchors. Through inorganic ionic polymerization, hydroxyapatite nanorivets are generated to anchor PVA chains, forming a hierarchically integrated organic–inorganic composite network. This unique riveting network structure imparts record‐breaking ultrahigh toughness (696.4 ± 119.1 MJ m − 3 ) and high strength (58.02 ± 3.87 MPa) to the resulting PVA/CPO eutectogels, significantly surpassing existing gel materials. Moreover, the PVA/CPO eutectogels demonstrate excellent energy absorption and dissipation, outstanding fatigue resistance over 8000 cycles, and the capacity for damage repair via secondary inorganic ionic polymerization. Consequently, PVA/CPO eutectogels exhibit significant potential for technological applications. The proposed IIP‐APN strategy provides a powerful platform for the design and development of high‐performance gel materials.