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Abstract Vinylogous urethane (VU_O) based polymer networks are widely used as catalyst‐free vitrimers that show rapid covalent bond exchange at elevated temperatures. In solution, vinylogous ureas (VU_N) undergo much faster bond exchange than VU_Oand are highly dynamic at room temperature. However, this difference in reactivity is not observed in their respective dynamic polymer networks, as VU_Oand VU_Nvitrimers prepared herein with very similar macromolecular architectures show comparable stress relaxation and creep behavior. However, by using mixtures of VU_Oand VU_Nlinkages within the same network, the dynamic reactions can be accelerated by an order of magnitude. The results can be rationalized by the effect of intermolecular hydrogen bonding, which is absent in VU_Ovitrimers, but is very pronounced for vinylogous urea moieties. At low concentrations of VU_N, these hydrogen bonds act as catalysts for covalent bond exchange, while at high concentration, they provide a pervasive vinylogous urea ‐ urethane (VU) network of strong non‐covalent interactions, giving rise to phase separation and inhibiting polymer chain dynamics. This offers a straightforward design principle for dynamic polymer materials, showing at the same time the possible additive and synergistic effects of supramolecular and dynamic covalent polymer networks. 

Dynamic covalent bonds in suspensions serve as effective friction, leading to shear-thickening behavior. This behavior is similar to that of physically contacting particles but shows a distinct dependence on particle size. 

Pluripotency, which is defined as a system not fixed as to its developmental potentialities, is typically associated with biology and stem cells. Inspired by this concept, we report synthetic polymers that act as a single “pluripotent” feedstock and can be differentiated into a range of materials that exhibit different mechanical properties, from hard and brittle to soft and extensible. To achieve this, we have exploited dynamic covalent networks that contain labile, dynamic thia-Michael bonds, whose extent of bonding can be thermally modulated and retained through tempering, akin to the process used in metallurgy. In addition, we show that the shape memory behavior of these materials can be tailored through tempering and that these materials can be patterned to spatially control mechanical properties.