Tough PEGgels by In Situ Phase Separation for 4D Printing

Polymer gels, consisting of cross‐linked polymer network systems swollen by a solvent, show great potential in biomedicine, flexible electronics, and artificial muscles, due to their tissue‐like mechanical properties. Due to the presence of a large amount of solvent, the improvement of the mechanical properties of the polymer gel is a challenge. Moreover, combining high toughness with useful properties, such as 3D printability or shape‐memory, in one polymer gel system is even more challenging. In this study, a simple and efficient method is developed for the fabrication of tough polymer gels by polymerizing 2‐hydroxyethyl methacrylate (HEMA) in a mixture of poly(ethylene glycol) (PEG) and poly(propylene glycol) (PPG). The polymerized elastic networkpresents distinct compatibility with PEG (compatible) and PPG (poorly compatible), resulting in in‐situ phase separation at the microscale. The resulting phase‐separated gel demonstrates high strength (8.0 MPa), favorable fracture strain (430%), and large toughness (17.0 MJ m−3). The separated hard phasewith a high glass transition temperature (75 °C) endows the whole soft polymer gel with the property of shape memory at room temperature. Finally, the fabrication of tunable tough PEGgels is combined with 3D printing as well as with shape memory properties, demonstrating the use of PEGgels for 4D printing. An efficient solvent strategy is proposed to enhance and refine the performance of polymer gel based on phase separation via adjusting the ratio of good and poor solvents. The separated hard phases endow the whole soft polymer gel shape‐memory property, further demonstrated as 4D printing.