Molecular design of polymer coatings capable of photo‐triggered stress relaxation via dynamic covalent bond exchange

Abstract Polymer coatings are frequently used to modify surface properties of inorganic substrates. However, the disparity in physical properties between polymer film and substrate often leads to residual stress development, which can be deleterious to the overall performance of coated materials. This work reports the molecular design of polymer films that dissipate stress upon irradiation with ultraviolet (UV) light. These polymers are synthesized by post‐polymerization modification of the reactive polymer, poly(2‐vinyl‐4,4‐dimethyl azlactone), to introduce dynamic crosslinks capable of light‐initiated addition transfer fragmentation chemistry. Using a custom‐built optical cantilever, contrasting film stress responses are observed between films containing dynamic bonds and analogous control films after UV light irradiation, which indicate successful stress relaxation. Further experiments demonstrate the complete relaxation of residual stress in dynamic films after an extended exposure, thereby generating a “stress‐free” film. Films fabricated using this approach can be easily tailored to incorporate additional moieties to introduce desired surface properties for future application in a wide array of coatings.