Physically Entangled Antiswelling Hydrogels with High Stiffness

Abstract Physically cross‐linked hydrogels have great potential for tissue engineering because of their excellent biocompatibility and easy fabrication. However, physical cross‐linking points are typically weaker compared to chemical ones and therefore cannot form robust hydrogels with excellent water stability, which greatly hinder their further applications. In this work, a novel hydrogel with high stiffness and outstanding antiswelling performance cross‐linked by hydrophobic polymer chains entanglements is reported. The hydrophobic polymer polyimide (PI) is mixed with the hydrophilic polymer poly‐(vinyl pyrrolidone) (PVP) to form cross‐linking points between the chains. At the equilibrium swelling state, tensile modulus of the hydrogel can be up to 22.57 MPa (higher than most existing hydrogels) and the equilibrium water swelling ratio ( ESR ) can be as low as 125.0%. By decreasing the PI mass ratio, tensile modulus and ESR of the hydrogel can be tuned in a wide range from 22.57 to 0.005 MPa and 125.0% to 765.6%, respectively. Using PVP/PI solutions as inks, uniform structures and multi‐material structures are fabricated having mechanical properties close to cartilage through a direct ink writing 3D printing platform. This current work demonstrates that entangled PVP/PI hydrogels have excellent tailoring capabilities and are promising candidates for tissue engineering applications.