Chain Friction and Lubrication Balanced Ultra‐Tough Polyacrylates With Wide‐Span Switchable Stiffness for Strain‐Programmable Deformation

Abstract Natural mollusks perform complex mechanical actions through reversible large‐strain deformation and stiffness switching, which are challenging to achieve simultaneously in synthetic materials. Herein, it is shown that a set of polyacrylates designed according to a chain friction and lubrication balanced strategy shows ultra‐stretchability ( λ up to 324), high resilience (near 100% recovery at strain ≥ 100), and wide‐span stiffness switching (up to 2073 times). The typical emulsion polymerization method and casting technique are adopted to fabricate the polyacrylate films. Quaternary ammonium surfactants are used as the emulsifier and reserved in the polymer matrix to enhance the chain segment lubrication with their long alkyl group but improve the whole chain friction through the formation of nano‐eutectics. These polyacrylates undergo multimodal mechanical responses, including temperature‐ or time‐programmed deformation and load‐bearing like artificial muscles. This molecular design principle and synthetic method provide a robust platform for the fabrication of ultra‐tough polymers for soft robots with multiple customized functions.