Polymerization‐Induced Micelle Gelation

Self‐assembly of polymer micelles offers a novel pathway to supramolecular structures such as 1D nanowires, yet gelation behavior remains underexplored. We demonstrated a universal copolymerization strategy using acrylic acid and methyl methacrylate to fabricate micellar hydrogels. Initiator concentration critically regulates gelation, i.e., low concentrations enable isolated micelle polymerization into compact 3D networks at the gelation threshold. Dissipative particle dynamics simulations corroborate experimental findings, revealing that multiblock copolymer formation at low initiator levels facilitates inter‐micellar bridging via alternating hydrophilic/hydrophobic chains, while high concentrations yield diblock copolymers limited to isolated micelles. This facile approach enables scalable production of hydrogels for broad applications.