Controlled degradation of disulfide-based epoxy thermosets for extreme environments

Johnson, Lewis D.; Ledet, Eric H.; Huffman, Nicolas Daniel; Swarner, Stephanie L.; Shepherd, Sarah D.; Durham, Phillip G.; Rothrock, Ginger

doi:10.1016/j.polymer.2015.03.020

Cited by 92 publications

(70 citation statements)

References 38 publications

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“…However, the epoxy monomers they used were petroleum‐based DGEBA, and these vitrimers should be reprocessed at extremely high temperature and be degraded in organic solvent with the aid of 2‐mercaptoethanol. Our dynamic epoxy resins thus possess several distinguished characteristics, such as (1) the easy preparation process from renewable epoxy monomer and commercially available aromatic disulfide, (2) the short stress relaxation time at moderate temperatures (behave as vitrimer) without any additives and catalysts because of the fast metathesis of disulfide bonds, and (3) the capability of being degraded to bioresource again in alkaline aqueous solution in contrast to previously reported organic solvents, which was greatly beneficial to environmental conservation. In addition, it is found that the bio‐based epoxy resins exhibited shape‐memory effect, and the shape recovery could be readily controlled by the extent of stress relaxation in the crosslinked network, thus allowed controlled shape change.…”

Section: Introductionmentioning

confidence: 99%

Bio‐based epoxy vitrimers: Reprocessibility, controllable shape memory, and degradability

Wang

Zhu

et al. 2017

J. Polym. Sci. Part A: Polym. Chem.

206

147

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The research activities in the development of recyclable and reprocessable covalently crosslinked networks, and the construction of polymers from renewable resources are both stemmed from the economical and environmental problems associated with traditional thermosets. However, there is little effort in combination of these two attractive strategies in material designs. This article reported a bio‐based vitrimer constructed from isosorbide‐derived epoxy and aromatic diamines containing disulfide bonds. The resulted dynamic epoxy resins showed comparable thermomechanical properties as compared to similar epoxy networks cured by traditional curing agent. Rheological tests demonstrated the fast stress relaxation of the dynamic network due to the rapid metathesis of disulfide bonds at temperature higher than glass transition temperature. This feature permitted the recycling and reprocessing of the fragmented samples for several times by hot press. The dynamic epoxy resins also exhibited shape‐memory effect, and it is demonstrated that the shape recovery ratio could be readily adjusted by controlling the stress relaxation in the temporary state at programming temperature. Moreover, the degradability of the dynamic epoxy resins in alkaline aqueous solution was also demonstrated. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017, 55, 1790–1799

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Section: Introductionmentioning

confidence: 99%

Bio‐based epoxy vitrimers: Reprocessibility, controllable shape memory, and degradability

Wang

Zhu

et al. 2017

J. Polym. Sci. Part A: Polym. Chem.

206

147

View full text Add to dashboard Cite

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“…The recent development of novel polymers with dynamic exchange reaction (ER) enables thermosets dissolution under mild conditions. [6][7][8][9][10][11][12] The dynamic bonds activated by a specic stimulus or chemicals lead to network rearrangement and selective bond cleavage. [13][14][15][16] These dynamic polymers have the desirable attributes of conventional thermosets, but also have more attractive attributes, such as self-healing and reprocessing of thermosets.…”

Section: Introductionmentioning

confidence: 99%

Dissolution of epoxy thermosets via mild alcoholysis: the mechanism and kinetics study

et al. 2018

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“…In this sense, aromatic disulfides are found to be especially promising, and exchange reactions have been reported at room temperature both in solution and in the solid state . Thus, aromatic disulfides have been used for the preparation of self‐healing and reprocessable elastomers, epoxy networks, or polyurethanes, among others.…”

Section: Introductionmentioning

confidence: 99%

Sulfenamides as Building Blocks for Efficient Disulfide‐Based Self‐Healing Materials. A Quantum Chemical Study

et al. 2018

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The theoretical self‐healing capacity of new sulfenamide‐based disulfides is estimated by using theoretical methods of quantum chemistry. Starting from previously studied aromatic disulfides, the influence of inserting a NH group between the disulfide and the phenyl ring (forming the sulfenamide), as well as the role of the phenyl ring in the self‐healing process is analyzed. Three parameters are used in the evaluation of the self‐healing capacity: i) the probability to generate sulfenyl radicals, which is the first step of the process; ii) the effect of the hydrogen bonding, which affects the mobility of the chains; and iii) the height of the exchange reaction barrier. The insertion of the NH group notably decreases the bond dissociation energy and, therefore, increases the probability to produce sulfenyl radicals and helps the approach of these radicals to neighboring disulfides, favoring the self‐healing process. The role of the phenyl rings is clearly observed in the reaction barriers, where the π–π stacking interactions notably stabilize the transition states, resulting in larger rate constants. Nevertheless, this stabilization is somewhat reduced in the aromatic sulfenamides, owing to a less effective π–π interaction. Therefore, the sulfenamide‐based aromatic disulfides may be considered as promising candidates for the design of efficient self‐healing materials.

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Controlled degradation of disulfide-based epoxy thermosets for extreme environments

Cited by 92 publications

References 38 publications

Bio‐based epoxy vitrimers: Reprocessibility, controllable shape memory, and degradability

Bio‐based epoxy vitrimers: Reprocessibility, controllable shape memory, and degradability

Dissolution of epoxy thermosets via mild alcoholysis: the mechanism and kinetics study

Sulfenamides as Building Blocks for Efficient Disulfide‐Based Self‐Healing Materials. A Quantum Chemical Study

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