Turning Vulcanized Natural Rubber into a Self-Healing Polymer: Effect of the Disulfide/Polysulfide Ratio

• Published in: ACS sustainable chemistry & engineering 2016-10, Vol.4 (10), p.5776-5784
• Main Authors: Hernández, Marianella, Grande, Antonio M, Dierkes, Wilma, Bijleveld, Johan, van der Zwaag, Sybrand, García, Santiago J
• Format: Article
• Language: English
• ISSN: 2168-0485; 2168-0485
• DOI: 10.1021/acssuschemeng.6b01760

A self-healing sulfur vulcanized natural rubber (NR) is here reported using the common ingredients in a traditional NR formulation. The dynamic character of the di- and polysulfide bonds naturally present in covalently cross-linked rubbers was found to be responsible for the healing ability and the full recovery of mechanical properties at moderate temperatures provided the material was employed in a nonfully cured starting state. Results show that a compromise between mechanical performance and healing capability can be reached by tailoring the amount of sulfur, the cross-linking density, and the disulfide/polysulfide ratio. The healing efficiency was found to depend on the postcuring storage time, the time between damage creation and re-establishment of mechanical contact, and the actual healing time. Furthermore, a dedicated electron spin resonance (ESR) test allowed establishing the underlying healing principle based on temperature-induced free sulfur radicals. The main observations presented here can serve as the basis for the design and preparation of other self-healing polymers with long-term durability based on di-/polysulfide bridges and other reversible moieties.