Rigid and Strong Thermoresponsive Shape Memory Hydrogels Transformed from Poly(vinylpyrrolidone-co-acryloxy acetophenone) Organogels

Shape memory hydrogels (SMHs) have a wide range of potential practical applications. However, the mechanically weak and soft nature of most SMHs strongly impedes their applications. Here, we report a novel kind of thermal-responsive SMH with high tensile strength and high elastic moduli. Organogels are first prepared by the copolymerization of a hydrophilic monomer N-vinylpyrrolidone (NVP) and a hydrophobic monomer acryloxy acetophenone (AAP) in N,N′-dimethylformamide (DMF) solutions, and then, poly(vinylpyrrolidone-co-acryloxy acetophenone) [poly(NVP-co-AAP)] hydrogels are obtained by solvent exchange with water. Because of the strong and reversible hydrophobic association and π–π stacking of acetophenone groups, the poly(NVP-co-AAP) hydrogels exhibit tensile strengths up to 8.41 ± 0.83 MPa and Young’s moduli up to 94.2 ± 1.3 MPa, which are more than 1 or 3 orders of magnitude higher than those of the organogels, respectively. The poly(NVP-co-AAP) hydrogels exhibit good shape memory behaviors, with a complete fixation ratio and a recovery ratio of 74–89%, as well as very fast shape-fixing and recovering rates (in seconds). These rigid and strong hydrogels are demonstrated to be an ideal shape memory material for surgical fixation devices to wrap around and support various shapes of limbs.