title: The underlying mechanisms for self-healing of poly(disulfide)s.
abstract: Recently, self-healing polymers based on disulfide compounds have gained attention due to the versatile chemistry of disulfide bonds and easy implementation into polymeric materials. However, the underlying mechanisms of disulfide exchange which induce the self-healing effect in poly(disulfide)s remain unclear. In this work, we elucidate the process of disulfide exchange using a variety of spectroscopic techniques. Comparing a model exchange reaction of 4-aminophenyl disulfide and diphenyl disulfide with modified reactions in the presence of additional radical traps or radical sources confirmed that the exchange reaction between disulfide compounds occurred via a radical-mediated mechanism. Furthermore, when investigating the effect of catalysts on the model exchange reaction, it could be concluded that catalysts enhance the disulfide exchange reaction through the formation of S-based anions in addition to the radical-mediated mechanism.
authors.affiliation: POLYMAT, University of the Basque Country UPV/EHU, Joxe Mari Korta Center, Avenida Tolosa 72, 20018 Donostia-San Sebastián, Spain. jm.asua@ehu.es.
authors.forename: Sil
authors.initials: S
authors.lastname: Nevejans
authors.affiliation: POLYMAT, University of the Basque Country UPV/EHU, Joxe Mari Korta Center, Avenida Tolosa 72, 20018 Donostia-San Sebastián, Spain. jm.asua@ehu.es.
authors.forename: Nicholas
authors.initials: N
authors.lastname: Ballard
authors.affiliation: SGIker, NMR Facility, University of the Basque Country UPV/EHU, Spain.
authors.forename: José I
authors.identifier: http://orcid.org/0000-0002-7646-6857
authors.initials: JI
authors.lastname: Miranda
authors.affiliation: Dispersions and Colloidal Materials, BASF SE, 67056 Ludwigshafen, Germany.
authors.forename: Bernd
authors.initials: B
authors.lastname: Reck
authors.affiliation: POLYMAT, University of the Basque Country UPV/EHU, Joxe Mari Korta Center, Avenida Tolosa 72, 20018 Donostia-San Sebastián, Spain. jm.asua@ehu.es.
authors.forename: José M
authors.initials: JM
authors.lastname: Asua