Vinylogous urethane (VUO) based polymer networks are widely used as catalyst‐free vitrimers that show rapid covalent bond exchange at elevated temperatures. In solution, vinylogous ureas (VUN) undergo much faster bond exchange than VUOand are highly dynamic at room temperature. However, this difference in reactivity is not observed in their respective dynamic polymer networks, as VUOand VUNvitrimers prepared herein with very similar macromolecular architectures show comparable stress relaxation and creep behavior. However, by using mixtures of VUOand VUNlinkages 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 VUOvitrimers, but is very pronounced for vinylogous urea moieties. At low concentrations of VUN, 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.
Materials with tunable modulus, viscosity, and complex viscoelastic spectra are crucial in applications such as self-healing, additive manufacturing, and energy damping. It is still challenging to predictively design polymer networks with hierarchical relaxation processes, as many competing factors affect dynamics. Here, networks with both pendant and telechelic architecture are synthesized with mixed orthogonal dynamic bonds to understand how the network connectivity and bond exchange mechanisms govern the overall relaxation spectrum. A hydrogen-bonding group and a vitrimeric dynamic crosslinker are combined into the same network, and multimodal relaxation is observed in both pendant and telechelic networks. This is in stark contrast to similar networks where two dynamic bonds share the same exchange mechanism. With the incorporation of orthogonal dynamic bonds, the mixed network also demonstrates excellent damping and improved mechanical properties. In addition, two relaxation processes arise when only hydrogen-bond exchange is present, and both modes are retained in the mixed dynamic networks. This work provides molecular insights for the predictive design of hierarchical dynamics in soft materials.
more » « less- NSF-PAR ID:
- 10473434
- Publisher / Repository:
- Nature Publishing Group
- Date Published:
- Journal Name:
- Nature Communications
- Volume:
- 14
- Issue:
- 1
- ISSN:
- 2041-1723
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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