Solvent‐Tuned DLP 3D‐Printed PNVCL Hydrogels With Enhanced Thermoresponse

ABSTRACT The development of Poly(N‐vinylcaprolactam) (PNVCL)‐based hydrogels for additive manufacturing remains challenging due to the difficulty of simultaneously achieving printability and enhanced thermoresponsive performance. Herein, chemically crosslinked P(NVCL‐DVA) organohydrogels (DVA, 3,9‐divinyl‐2,4,8,10‐tetraoxaspiro[5.5]undecane) were prepared using diethylene glycol (DEG) as a cosolvent with water and fabricated by digital light processing (DLP) 3D printing, followed by solvent exchange with water. The influence of formulation parameters, particularly DEG content, on network formation and thermoresponsive behavior was systematically investigated. The optimized hydrogels exhibited interconnected porous structures associated with high water uptake, enhanced deswelling amplitude, and rapid deswelling and reswelling kinetics. Collectively, these findings establish an effective formulation strategy that expands the potential of PNVCL‐based materials for DLP 3D printing.