Stiffness Variable Polymers Comprising Phase‐Changing Side‐Chains: Material Syntheses and Application Explorations

Stiffness variable materials have been applied in a variety of engineering fields that require adaptation, automatic modulation, and morphing because of their unique property to switch between a rigid, load-bearing state and a soft, compliant state. Stiffness variable polymers comprising phase-changing side-chains (s-SVPs) have densely grafted, highly crystallizable long alkyl side-chains in a crosslinked network. Such a bottlebrush network-like structure gives rise to rigidity modulation as a result of the reversible crystallization and melting of the side chains. The corresponding modulus changes can be more than 1000-fold within a narrow temperature span, from ≈102 MPa to ≈102 kPa or lower. Other important properties of the s-SVP, such as stretchability, optical transmittance, and adhesion, can also be altered. This work reviews the underlying molecular mechanisms in the s-SVP's, discusses the material's structure-property relationship, and summarizes important applications explored so far, including reversible shape transformation, bistable electromechanical transduction, optical modulation, and reversible adhesion.