Increasing Inter‐Micellar Connectivity Toughens and Imparts Cooling‐Induced Shape Memory in Micellar Hydrogels

ABSTRACT Micellar gels formed by self‐assembling block copolymers have advanced applications spanning drug delivery, biofabrication, and soft robotics. However, their broader use as crosslinked hydrogels is limited by the challenge of simultaneously tuning their mechanical properties and stimuli‐responsive behaviors while maintaining the ability to process the pre‐hydrogel through techniques like extrusion. Here, we show that oligomerization of Pluronic triblock copolymers provides a single tunable parameter, the oligomer fraction, , for modulating the inter‐micellar connectivity and mechanical properties of Pluronic hydrogels. Increasing produces hydrogels spanning brittle to highly extensible responses. Coarse‐grained molecular dynamics simulations reveal that oligomerized Pluronic chains bridge multiple micelles, forming highly interconnected networks. Since oligomerization maintains the micellar network architecture of high‐ hydrogels, we demonstrate a cooling‐induced, reverse thermal shape‐memory behavior in which plastic deformation at room temperature is reversed upon cooling below Pluronic's lower critical solution temperature. Oligomerization also preserves the printability of Pluronic gels, enabling anisotropic hydrogels with spatially programmable mechanical properties via embedded 3D printing. Graph‐theoretic analyses of simulated networks establish intermicellar connectivity as a key structural parameter governing mechanical tunability. These results present oligomerization as a versatile processing strategy for tuning mechanical and responsive properties of micellar hydrogels.