Unexpectedly large entropic barrier controls bond rearrangements in vitrimers
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arXiv
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| Hauptverfasser: | , , , , |
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| Format: | Preprint |
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2025
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| _version_ | 1866912532259667968 |
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| author | Cheng, Shinian Rey, Lilliana Yao, Beibei Popov, Ivan Sokolov, Alexei P. |
| author_facet | Cheng, Shinian Rey, Lilliana Yao, Beibei Popov, Ivan Sokolov, Alexei P. |
| contents | Vitrimers are a relatively new class of polymeric materials containing associative covalent dynamic bonds that make them recyclable by design. However, the fundamental mechanisms controlling their viscoelastic properties remain poorly understood. Our detailed studies of relaxation dynamics and viscoelastic behavior of model vitrimers revealed that the density of dynamic covalent crosslinks has no influence on chain dynamics (beyond a weak change in the glass transition temperature), yet it strongly affects the linear viscoelasticity of vitrimers. Increasing the crosslink density induces a sol-gel transition consistent with predictions of classical gelation theory, demonstrating its applicability to vitrimers. Remarkably, the temperature-dependent analysis of the bond rearrangement time reveals an unexpectedly large negative activation entropy in the transition state that strongly slows down the bond exchange process despite its relatively low activation enthalpy. This insight explains the unusual long timescale for bond rearrangement in vitrimers and highlights the significance of entropy in controlling the viscoelasticity of dynamic covalent networks. |
| format | Preprint |
| id |
arxiv_https___arxiv_org_abs_2508_05824 |
| institution | arXiv |
| publishDate | 2025 |
| record_format | arxiv |
| spellingShingle | Unexpectedly large entropic barrier controls bond rearrangements in vitrimers Cheng, Shinian Rey, Lilliana Yao, Beibei Popov, Ivan Sokolov, Alexei P. Soft Condensed Matter Materials Science Vitrimers are a relatively new class of polymeric materials containing associative covalent dynamic bonds that make them recyclable by design. However, the fundamental mechanisms controlling their viscoelastic properties remain poorly understood. Our detailed studies of relaxation dynamics and viscoelastic behavior of model vitrimers revealed that the density of dynamic covalent crosslinks has no influence on chain dynamics (beyond a weak change in the glass transition temperature), yet it strongly affects the linear viscoelasticity of vitrimers. Increasing the crosslink density induces a sol-gel transition consistent with predictions of classical gelation theory, demonstrating its applicability to vitrimers. Remarkably, the temperature-dependent analysis of the bond rearrangement time reveals an unexpectedly large negative activation entropy in the transition state that strongly slows down the bond exchange process despite its relatively low activation enthalpy. This insight explains the unusual long timescale for bond rearrangement in vitrimers and highlights the significance of entropy in controlling the viscoelasticity of dynamic covalent networks. |
| title | Unexpectedly large entropic barrier controls bond rearrangements in vitrimers |
| topic | Soft Condensed Matter Materials Science |
| url | https://arxiv.org/abs/2508.05824 |