Self‐Evolution of High Mechanical Strength Dry‐Network Polythiourethane Thermosets into Neat Macroscopic Hollow Structures

Organism-inspired hollow structures are attracting increasing interest for the construction of various bionic functional hollow materials. Next-generation self-evolution hollow materials tend to combine simple synthesis, high mechanical strength, and regular shape. In this study, we designed and synthesized a novel dry-network polythiourethane thermoset with excellent mechanical performance. The polymer film could evolve into a neat and well-organized object with a macroscopic hollow interior structure after being immersed in an aqueous NaOH solution. The self-evolution hollow structure originated from a hydrogen-bonded polymer network, which was later transformed into a network bearing both hydrogen bonds and ionic bonds. The swelling and thickness growth of this material could be controlled by the NaOH concentration and the immersion time. This unique self-evolution behavior was further utilized to produce a series of macroscopic 3D hollow-containing molds, which could be potentially applied in the production of smart materials.