Thiol–Anhydride Dynamic Reversible Networks

Podgórski, Maciej; Mavila, Sudheendran; Huang, Sijia; Spurgin, Nathan; Sinha, Jasmine; Bowman, Christopher N.

doi:10.1002/anie.202001388

Cited by 71 publications

(54 citation statements)

References 32 publications

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“…Dynamic covalent bonding features reversible covalent bond breaking and formation with external stimuli, such as light, temperature, mechanical stress, etc 63–68 . According to a previous review, 65 several covalent bonds, including CC, CN, CO, SC, SS bonds, have been reported to undergo reversible dynamic covalent bonding exchanges.…”

Section: Covalent Adaptable Networkmentioning

confidence: 99%

“…Dynamic covalent bonding features reversible covalent bond breaking and formation with external stimuli, such as light, temperature, mechanical stress, etc. [63][64][65][66][67][68] According to a previous review, 65 several covalent bonds, including C C, C N, C O, S C, S S bonds, have been reported to undergo reversible dynamic covalent bonding exchanges. Because of this feature, significant efforts have applied dynamic covalent bonding to synthesize two-and three-dimensional covalent molecules with different size, geometry and functionality.…”

Section: Covalent Adaptable Networkmentioning

confidence: 99%

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Recent advances to decrease shrinkage stress and enhance mechanical properties in free radical polymerization: a review

Fang

Guymon

2021

Polymer International

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Free radical polymerizations have been widely used for a variety of applications, including coating, packaging, adhesives, inks and dental materials. However, shrinkage stress in network systems due to volumetric shrinkage during polymerization often results in poor mechanical performance of final materials, often limiting end use. Delaying gelation during polymerization while incorporating functional structure or functionalized groups into the polymer networks may lead to significantly reduced shrinkage stress and, consequently, enhanced thermomechanical properties. In this review, we summarize several practical methods, including thiol–ene radical polymerization, addition–fragmentation chain transfer, controlled radical polymerization, covalent adaptable networks, ring‐opening polymerization and cyclopolymerization, that have shown promise in reducing volumetric shrinkage and associated stress in network‐forming systems. The resulting enhanced (thermo)mechanical material properties of these modified polymers are also introduced. These methods have proven to be powerful tools for fabricating polymers with novel functionality and properties and thereby show potential to expand application of free radical thermoset materials. © 2021 Society of Industrial Chemistry.

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Section: Covalent Adaptable Networkmentioning

confidence: 99%

Section: Covalent Adaptable Networkmentioning

confidence: 99%

Recent advances to decrease shrinkage stress and enhance mechanical properties in free radical polymerization: a review

Fang

Guymon

2021

Polymer International

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“…To fabricate liquid‐crystalline elastomers capable of thermally stable, permanent retention of phototropic actuation, materials were prepared by using C6M, allyl succinic anhydride–hexane dithiol (ASA‐HDT), and a diarylethene (DAE) diacrylate monomer (Figure 1). The DAE and ASA‐HDT monomers were synthesized following prior reports [22, 34] . Components were mixed at a thiol:acrylate functional group ratio of 1 : 0.75 and 15 wt% DAE monomer.…”

Section: Resultsmentioning

confidence: 99%

Shape Permanence in Diarylethene‐Functionalized Liquid‐Crystal Elastomers Facilitated by Thiol‐Anhydride Dynamic Chemistry

et al. 2022

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Diarylethene‐functionalized liquid‐crystalline elastomers (DAE‐LCEs) containing thiol‐anhydride bonds were prepared and shown to undergo reversible, reprogrammable photoinduced actuation. Upon exposure to UV light, a monodomain DAE‐LCE generated 5.5 % strain. This photogenerated strain was demonstrated to be optically reversible over five cycles of alternating UV/Visible light exposure with minimal photochrome fatigue. The incorporation of thiol‐anhydride dynamic bonds allowed for retention of actuated states. Further, re‐programming of the nematic director was achieved by heating above the temperature for bond exchange to occur (70 °C) yet below the nematic‐to‐isotropic transition temperature (100 °C) such that order was maintained between mesogens. The observed thermal stability of each of the diarylethene isomers of over 72 h allowed for decoupling of photo‐induced processes and polymer network effects, showing that both polymer relaxation and back‐isomerization of the diarylethene contributed to LCE relaxation over a period of 12 hours after actuation unless bond exchange occurred.

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“…To overcome the abovementioned problems, the latest generation of self-healing glassy thermoset polymers introduce various dynamic covalent bonds within the cross-linked network. − The resultant covalent adaptive network can reorganize by thermally or chemically triggering the reversible reactions and thus endowing the polymer with intrinsic multiple self-healing ability and recyclability. The rearrangement and reorganization of covalent adaptive networks heavily depend on both high molecular mobility and high activity of reversible bonds. , The former makes cleaved moieties rapidly find their counterparts, and the latter can accelerate the formation of new bonds.…”

Section: Introductionmentioning

confidence: 99%

Room-Temperature Self-Healable and Mechanically Robust Thermoset Polymers for Healing Delamination and Recycling Carbon Fibers

Feng

2021

ACS Appl. Mater. Interfaces

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The advocacy of carbon neutrality and circular economy encourages people to pursue self-healing and recycling of glassy thermoset polymers in a more realistic and energy-saving manner, the best being intrinsic healing under room temperature. However, the high mechanical robustness and healing ability are mutually exclusive because of their completely opposite requirements for the mobility of the polymer networks. Here, we report a dual-cross-linked network by slightly coupling the lowmolecular-weight branched polyethylenimine with an ester-containing epoxy monomer in a nonstoichiometric proportion. The highly mobile and dense noncovalent hydrogen bonds at the chain branches and ends can not only complement the mechanical robustness (tensile strength of 61.6 MPa, elastic modulus of 1.6 GPa, and toughness of 19.2 MJ/m 3 ) but also endow the glassy thermoset polymer (T g > 40 °C) with intrinsic self-healing ability (healing efficiency > 84%) at 20 °C. Moreover, the resultant covalent adaptive network makes the thermoset polymer stable to high temperatures and solvents, yet it is readily dissolved in ethylene glycol through internal catalyzed transesterification. The application to room temperature delamination healing and carbon fiber recycling was demonstrated as a proof-of-concept.

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Thiol–Anhydride Dynamic Reversible Networks

Abstract: Supporting information and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.

Cited by 71 publications

References 32 publications

Recent advances to decrease shrinkage stress and enhance mechanical properties in free radical polymerization: a review

Recent advances to decrease shrinkage stress and enhance mechanical properties in free radical polymerization: a review

Shape Permanence in Diarylethene‐Functionalized Liquid‐Crystal Elastomers Facilitated by Thiol‐Anhydride Dynamic Chemistry

Room-Temperature Self-Healable and Mechanically Robust Thermoset Polymers for Healing Delamination and Recycling Carbon Fibers

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