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The development of vitrimers with dynamic covalent bonds enables reprocessability in crosslinked networks, offering a sustainable alternative to conventional thermosets. In this work, a thiol-acrylate vitrimer was synthesized from lignin-derivable (bis)phenols (guaiacol and bisguaiacol F) and compared to a control derived from petroleum-based precursors (phenol and bisphenol F) to investigate the effect of structural differences on network properties and thermal reprocessing. The presence of methoxy groups in the lignin-derivable vitrimer promoted intermolecular interactions by serving as additional hydrogen bonding acceptors during curing, leading to a denser network, as evidenced by a higher rubbery storage modulus (∼2.4 MPa vs. ∼1.4 MPa) and glass transition temperature (∼34 °C vs. ∼28 °C). The lignin-derivable vitrimer exhibited a slightly higher elongation-at-break (∼170% vs. ∼130%) and improved mechanical robustness, including a nearly two-fold increase in Young's modulus (∼6.9 MPa vs. ∼3.4 MPa) and toughness (∼750 kJ m−3vs. ∼390 kJ m−3). The similar stress relaxation behavior and activation energy of viscous flow indicated comparable bond exchange dynamics between the two vitrimers, while the lignin-derivable system demonstrated higher thermal healing efficiency with improved recovery of tensile properties after reprocessing. These findings highlight the potential of lignin-based aromatics in designing mechanically robust and sustainable vitrimers, aligning with efforts to develop renewable and reprocessable polymeric materials.
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The nonequilibrium behaviors of covalent adaptable network polymers during the topology transition
Vitrimers with bond exchange reactions (BERs) are a class of covalent adaptable network (CAN) polymers at the forefront of recent polymer research. They exhibit malleable and self-healable behaviors and combine the advantages of easy processability of thermoplastics and excellent mechanical properties of thermosets. For thermally sensitive vitrimers, a molecular topology melting/frozen transition is triggered when the BERs are activated to rearrange the network architecture. Notable volume expansion and stress relaxation are accompanied, which can be used to identify the BER activation temperature and rate as well as to determine the malleability and interfacial welding kinetics of vitrimers. Existing works on vitrimers reveal the rate-dependent behaviors of the nonequilibrium network during the topology transition. However, it remains unclear what the quantitative relationship with heating rate is, and how it will affect the macroscopic stress relaxation. In this paper, we study the responses of an epoxy-based vitrimer subjected to a change in temperature and mechanical loading during the topology transition. Using thermal expansion tests, the thermal strain evolution is shown to depend on the temperature-changing rate, which reveals the nonequilibrium states with rate-dependent structural relaxation. The influences of structural relaxation on the stress relaxation behaviors are examined in both uniaxial tension and compression modes. Assisted by a theoretical model, the study reveals how to tune the material and thermal-temporal conditions to promote the contribution of BERs during the reprocessing of vitrimers.
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- Award ID(s):
- 1901807
- PAR ID:
- 10282281
- Date Published:
- Journal Name:
- Soft Matter
- Volume:
- 17
- Issue:
- 8
- ISSN:
- 1744-683X
- Page Range / eLocation ID:
- 2104 to 2119
- 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/10.1039/D0SM01471K
