Liquid crystalline elastomers programmed with light-activated bond exchange allowing controlled shape change.

The ability to behave in a fluidlike manner fundamentally separates thermoset and thermoplastic polymers. Bridging this divide, covalent adaptable networks (CANs) structurally resemble thermosets with permanent covalent crosslinks but are able to flow in a manner that resembles thermoplastic behavior only when a dynamic chemical reaction is active. As a consequence, the rheological behavior of CANs becomes intrinsically tied to the dynamic reaction kinetics and the stimuli that are used to trigger those, including temperature, light, and chemical stimuli, providing unprecedented control over viscoelastic properties. CANs represent a highly capable material that serves as a powerful tool to improve mechanical properties and processing in a wide variety of polymer applications, including composites, hydrogels, and shape-memory polymers. This review aims to highlight the enabling material properties of CANs and the applied fields where the CAN concept has been embraced.

Classical materials readily switch phases (solid to fluid or fluid to gas) upon changes in pressure or heat; however, subsequent reversion of the stimulus returns the material to their original phase. Covalently cross-linked polymer networks, which are solids that do not flow when strained, do not change phase even upon changes in temperature and pressure. However, upon the addition of dynamic cross-links, they become stimuli responsive, capable of switching phase from solid to fluid, but quickly returning to the solid state once the stimulus is removed. Reported here is the first material capable of a bistable switching of phase. A permanent solid to fluid transition or vice versa is demonstrated at room temperature, with inherent, spatiotemporal control over this switch in either direction triggered by exposure to light.