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One method to improve the properties of covalent adaptable networks (CANs) is to reinforce them with a fraction of permanent cross‐links without sacrificing their (re)processability. Here, a simple method to synthesize poly(n‐hexyl methacrylate) (PHMA) and poly(n‐lauryl methacrylate) (PLMA) networks containing static dialkyl disulfide cross‐links (utilizing bis(2‐methacryloyl)oxyethyl disulfide, or DSDMA, as a permanent cross‐linker) and dynamic dialkylamino sulfur‐sulfur cross‐links (utilizing BiTEMPS methacrylate as a dissociative dynamic covalent cross‐linker) is presented. The robustness and (re)processability of the CANs are demonstrated, including the full recovery of cross‐link density after recycling. The authors also investigate the effect of static cross‐link content on the stress relaxation responses of the CANs with and without percolated, static cross‐links. As PHMA and PLMA have very different activation energies of their respective cooperative segmental mobilities, it is shown that the dissociative CANs without percolated, static cross‐links have activation energies of stress relaxation that are dominated by the dissociation of BiTEMPS methacrylate cross‐links rather than by the cooperative relaxations of backbone segments, i.e., the alpha relaxation. In CANs with percolated, static cross‐links, the segmental relaxation of side chains, i.e., the beta relaxation, is critical in allowing for large‐scale stress relaxation and governs their activation energies of stress relaxation.
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Internal Catalysis in Dynamic Hydrogels with Associative Thioester Cross-Links
Thioesters are an essential functional group in biosynthetic pathways, which has motivated their development as reactive handles in probes and peptide assembly. Thioester exchange is typically accelerated by catalysts or elevated pH. Here, we report the use of bifunctional aromatic thioesters as dynamic covalent cross-links in hydrogels, demonstrating that at physiologic pH in aqueous conditions, transthioesterification facilitates stress relaxation on the time scale of hundreds of seconds. We show that intramolecular hydrogen bonding is responsible for accelerated exchange, evident in both molecular kinetics and macromolecular stress relaxation. Drawing from concepts in the vitrimer literature, this system exemplifies how dynamic cross-links that exchange through an associative mechanism enable tunable stress relaxation without altering stiffness.
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- PAR ID:
- 10504975
- Publisher / Repository:
- American Chemical Society
- Date Published:
- Journal Name:
- ACS Macro Letters
- ISSN:
- 2161-1653
- Page Range / eLocation ID:
- 621 to 626
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1021/acsmacrolett.4c00245
