The underlying mechanisms for self-healing of poly(disulfide)s

Nevejans, Sil; Ballard, Nicholas; Miranda, José I.; Reck, Bernd; Asúa, José M.

doi:10.1039/c6cp04028d

Cited by 177 publications

(136 citation statements)

References 46 publications

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“…As stated in the Introduction, the prevalent mechanism of the self‐healing process in disulfide‐based materials is a [2+1] radical‐mediated mechanism, in which the generated sulfenyl radicals attack other disulfides found in the vicinity via a three‐membered transition state, as represented in Figure .…”

Section: Resultsmentioning

confidence: 99%

“…The mechanism responsible for the exchange of the disulfide compounds has recently been proposed theoretically by using quantun chemical calculations, and confirmed experimentally . It consists of a [2+1] radical‐mediated mechanism, in which the first step is the homolytic cleavage of the S−S bond to generate sulfenyl radicals that may attack other neighboring disulfide bonds, producing an interchange of sulfur atoms via a three‐membered transition state.…”

Section: Introductionmentioning

confidence: 99%

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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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Section: Resultsmentioning

confidence: 99%

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 plausible reason for delayed healing could be due to slow disulfide exchange reactions of aliphatic disulfides of PHMssEt-based gels, compared to the corresponding aromatic disulfides. [18,24] These results suggest that self-healing on microscale cuts in the dual crosslinked P5-COOH-based gels could occur in possibly dual mechanisms (i.e., disulfide exchange and metalligand interaction) at room temperate. At higher temperatures (i.e., 80 °C), dual healing could be facilitated due to an increased polymer motion.…”

Section: Resultsmentioning

confidence: 88%

“…Digital images of a penetrating cut with 0.1 cm wide and 0.7 cm long was completely healed in 20 h at 80 °C, suggesting that moderate temperature enabled rapid self‐healing by disulfide exchange reactions in this system (Figure S10b, Supporting Information). The plausible reason for delayed healing could be due to slow disulfide exchange reactions of aliphatic disulfides of PHMssEt‐based gels, compared to the corresponding aromatic disulfides . These results suggest that self‐healing on microscale cuts in the dual crosslinked P5‐COOH‐based gels could occur in possibly dual mechanisms (i.e., disulfide exchange and metal–ligand interaction) at room temperate.…”

Section: Resultsmentioning

confidence: 93%

Multiblock Copolymer-Based Dual Dynamic Disulfide and Supramolecular Crosslinked Self-Healing Networks

Noh

2017

Macromol. Rapid Commun.

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A new multiblock copolymer self-healing strategy is reported that centers on the synthesis of block copolymers designed with different self-healing motifs incorporated into individual blocks. As a proof of concept, a novel pentablock copolymer (ABCBA) consisting of a poly(ethylene glycol) middle block and self-healable symmetric blocks of a polymethacrylate with pendant disulfide linkages and carboxylic acids is synthesized by a combination of consecutive controlled radical polymerization with hydrolytic cleavage. Disulfide exchange reactions of pendant disulfide linkages and metal-ligand interactions of pendant carboxylic acids with ferric ions allow for the formation of dual crosslinked networks with dynamic disulfide and supramolecular crosslinkages. The resultant networks possessing self-healing viscoelasticity enable self-healing on macroscale damages through supramolecular metal-ligand interactions and disulfide exchange reactions at room or moderate temperatures. These preliminary results suggest that the strategy can offer the versatility in the development of multifunctional self-healable materials in dual or multiple self-healable mechanisms.

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“…The disulfide bond is one of the most intriguing dynamic bonds and widely used in dynamic covalent/combinatorial chemistry . The exchange reaction mechanism between disulfide compounds largely occurs via a radical‐mediated mechanism . Various stimulation conditions can facilitate this process, such as catalysts, light irradiation, ultrasonic, moderate temperature and external force .…”

Section: Introductionmentioning

confidence: 99%

Aromatic amine‐terminated polysulfide oligomer: Synthesis and application in self‐healable polyurea

Gao

Zuo

et al. 2019

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

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The dynamic chemistry of disulfide bonds has emerged as one of the most powerful tools used for the fabrication of organic compounds and self‐healing materials. In this article, a novel aromatic amine‐terminated polysulfide oligomer is first synthesized from thiol‐terminated polysulfide oligomer and bis(4‐aminophenyl) disulfide via disulfide metathesis mechanism. The resulting oligomer is confirmed by FTIR and 1H NMR spectra and then successfully applied in constructing self‐healable polyurea material (A‐LP23‐I), which combines the advantages of higher strength of polyureas and excellent self‐healing ability of polysulfide‐based materials. After subjecting to a temperature of 75 °C for 48 h, both the tensile strength and ultimate elongation of A‐LP23‐I restore to more than 90% of the original values (3.32 MPa and 396%). This study demonstrates a novel strategy for synthesizing aromatic amine‐terminated oligomer. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 1460–1466

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The underlying mechanisms for self-healing of poly(disulfide)s

Cited by 177 publications

References 46 publications

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

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

Multiblock Copolymer-Based Dual Dynamic Disulfide and Supramolecular Crosslinked Self-Healing Networks

Aromatic amine‐terminated polysulfide oligomer: Synthesis and application in self‐healable polyurea

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