“Catfish Effect”‐Inspired Hybrid Dynamic Polymer Networks with Fast Liquid‐Like Dynamics and Scalable Processability for Sustainable Electronics

Abstract Dynamic polymer networks hold promise for sustainable electronics, but their limited network dynamics hinder rapid, industrially‐scalable processing. Inspired by the biological “Catfish Effect”, molecular hybridization engineering is introduced to create hybrid dynamic polymer networks (HDPNs) with multiscale liquid‐like dynamics and rapid processability. By strategically integrating high‐mobility linear‐polymer chains (LPCs) as “molecular catfish” into precursor vitrimer networks through a bond dissociation–chain transfer–topology isomerization (BCT) mechanism, topologies featuring dual‐dynamic backbones and abundant dynamically‐active dangling chains (DCs) are engineered. This architecture accelerates network reconfiguration through synergistic molecular‐dynamics enhancement across both segment and chain scales. The collective fluidizing effect of DCs induces liquid‐like segmental dynamics even at lower temperatures, transforming segmental relaxation from non‐Arrhenius (Vogel–Fulcher–Tammann) to Arrhenius‐like, reducing relaxation times by ≈1000 fold over conventional networks. Simultaneously, active DC participation in dual‐dynamic bond exchanges, coupled with embedded LPCs, yields four‐fold faster chain reptation and stress relaxation, promoting solid‐to‐liquid transitions. Multiscale‐enhanced dynamics enable rapid, shape‐adaptive processing (including extrusion), high‐efficiency self‐repairing (>96%), and organic‐solvent‐free closed‐loop recycling. HDPN‐integrated sensors and energy harvesters demonstrate exceptional self‐repairability, durability, and near‐100% device‐to‐device recyclability. This versatile approach enables development of rapidly‐processable dynamic materials and upcycling of existing polymers into high‐value‐added adaptive systems for next‐generation electronics and beyond.