Fabrication of Tough Hydrogel Composites from Photoresponsive Polymers to Show Double-Network Effect

Inspired by the toughening mechanism of double-network (DN) gels, tough hydrogel composites with a sandwich structure were fabricated from photoresponsive polymers. By copolymerization of hydrophilic monomers, 2-ureidoethyl methacrylate (UM), and photoresponsive hydrophobic monomers, (2-nitrobenzyloxycarbonylaminoethyl methacrylate (NBOC)) at high concentrations, physical hydrogels that are soft and highly stretchable are formed due to the hydrophobic associations of NBOC, serving as dynamic crosslinkers. By UV irradiation, the physical crosslinking switches into chemical crosslinking, and the soft physical hydrogels transform into rigid and less stretchable chemical hydrogels. By UV curing the surface layers of the physical hydrogels, we prepared hydrogel composites having a sandwiched structure with two rigid outer layers and a soft inner layer. The molecular-level continuous interfaces and matched swelling ratios between the layers ensure the macroscale hydrogel composites' high strength and toughness with a DN gel effect. The outer layers fracture preferentially at deformation, playing a role like the first network of a DN gel, while the inner layer maintains the integrity, playing a role resembling the second network. The evolution of the fracture morphology of the rigid layers gives useful insight into the internal fracture process of DN gels.