Bitgaram Kim, Moonseok Jang, Zekai Wang and Ji-Hun Seo*,
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Synergistic Effects of Mechanical Topology and Chemical Exchange in Dynamic Covalent Networks Incorporated with Polyrotaxane
While dynamic covalent networks (DCNs) have garnered increasing attention as reprocessable thermosets, their mechanical and dynamic behaviors need further optimization. Most existing approaches rely on chemically tuning bond exchange reactions; however, the topological design of the network, particularly through the integration of mechanically interlocked bonds (MIBs), has not been systematically explored. In this study, we investigate the impact of polyrotaxane (PR)-based MIBs on the reconfigurability and mechanical performance of vinylogous urethane-based DCNs by designing networks with non-sliding (fixed) and sliding (PR-containing) polymers. The PR-based systems are further categorized according to their direct or indirect participation in amine exchange reactions. Incorporating PRs into DCNs significantly enhanced relaxation dynamics, reprocessability, and toughness. Among them, the DPRam network, featuring aminated PR capable of directly participating in the bond exchange, shows the lowest activation energy (85.3 kJ mol–1), the highest toughness retention (94.8%), the best reprocessing ability, and the fastest shape recovery. These advantages are attributed to the synergistic combination of slidable topology and dynamic covalent reactivity. This study highlights the potential of integrating PRs into a structural design strategy to advance topologically adaptive, high-performance DCN systems.
期刊介绍:
The journal Chemistry of Materials focuses on publishing original research at the intersection of materials science and chemistry. The studies published in the journal involve chemistry as a prominent component and explore topics such as the design, synthesis, characterization, processing, understanding, and application of functional or potentially functional materials. The journal covers various areas of interest, including inorganic and organic solid-state chemistry, nanomaterials, biomaterials, thin films and polymers, and composite/hybrid materials. The journal particularly seeks papers that highlight the creation or development of innovative materials with novel optical, electrical, magnetic, catalytic, or mechanical properties. It is essential that manuscripts on these topics have a primary focus on the chemistry of materials and represent a significant advancement compared to prior research. Before external reviews are sought, submitted manuscripts undergo a review process by a minimum of two editors to ensure their appropriateness for the journal and the presence of sufficient evidence of a significant advance that will be of broad interest to the materials chemistry community.