Stimuli-responsive polymers with complicated but controllable shape-morphing behaviors are critically desirable in several engineering fields. Among the various shape-morphing materials, cross-linked polymers with exchangeable bonds in dynamic network topology can undergo on-demand geometric change via solid-state plasticity while maintaining the advantageous properties of cross-linked polymers. However, these dynamic polymers are susceptible to creep deformation that results in their dimensional instability, a highly undesirable drawback that limits their service longevity and applications. Inspired by the natural ice strategy, which realizes creep reduction using crystal structure transformation, we evaluate a dynamic cross-linked polymer with tunable creep behavior through topological alternation. This alternation mechanism uses the thermally triggered disulfide–ene reaction to convert the network topology – from dynamic to static – in a polymerized bulk material. Thus, such a dynamic polymer can exhibit topological rearrangement for thermal plasticity at 130°C to resemble typical dynamic cross-linked polymers. Following the topological alternation at 180°C, the formation of a static topology reduces creep deformation by more than 85% in the same polymer. Owing to temperature-dependent selectivity, our cross-linked polymer exhibits a shape-morphing ability while enhancing its creep resistance for dimensional stability and service longevity after sequentially topological alternation. Our design enriches the design of dynamic covalent polymers, which potentially expands their utility in fabricating geometrically sophisticated multifunctional devices.
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