Sacrificial Mechanical Bond is as Effective as a Sacrificial Covalent Bond in Increasing Cross-Linked Polymer Toughness

Abstract

Sacrificial chemical bonds have been used effectively to increase the toughness of elastomers because such bonds dissociate at forces significantly below the fracture limit of the primary load-bearing bonds, thereby dissipating local stress. This approach owes much of its success to the ability to adjust the threshold force at which the sacrificial bonds fail at the desired rate, for example, by selecting either covalent or noncovalent sacrificial bonds. Here, we report experimental and computational evidence that a mechanical bond, responsible for the structural integrity of a rotaxane or a catenane, increases the elastomer’s fracture strain, stress, and energy as much as a covalent bond of comparable mechanochemical dissociation kinetics. We synthesized and studied 6 polyacrylates cross-linked by either difluorenylsuccinonitrile (DFSN), which is an established sacrificial mechanochromic moiety; a [2]­rotaxane, whose stopper allows its wheel to dethread on the same subsecond time scale as DFSN dissociates when either is under tensile force of 1.5–2 nN; a structurally homologous [2]­rotaxane with a much bulkier stopper that is stable at force >5.5 nN; similarly stoppered [3]­rotaxanes containing DFSN in their axles; and a control polymer with aliphatic nonsacrificial cross-links. Our data suggest that mechanochemical dethreading of a rotaxane without failure of any covalent bonds may be an important, hitherto unrecognized, contributor to the toughness of some rotaxane-cross-linked polymers and that sacrificial mechanical bonds provide a mechanism to control material fracture behavior independently of the mechanochemical response of the covalent networks, due to their distinct relationships between structure and mechanochemical reactivity.

TRPM4-Inspired Polymeric Nanochannels with Preferential Cation Transport for High-Efficiency Salinity-Gradient Energy Conversion

“…As shown in Figure S22, the stress–strain curves of membranes were measured at different stages, in which the tensile strength (22.7 MPa) and elongation at break (28.6%) of SPES-Na + /PIS-2% were both superior to pristine SPES-Na + membranes (16.8 MPa and 18.1%). The improvement of mechanical integrities was due to Na + –π interaction, which restricted the movement of polymer chains and acted as sacrificial bonds to dissipate external energy. , The CNMs possessed mechanical strength for further assembly and analysis. Subsequently, the ion transport behaviors of CNMs could be determined by current–voltage ( I – V ) curves using KCl solutions with various concentrations as electrolytes.…”

Mechanochemical Approaches to Fundamental Studies in Soft‐Matter Physics

“…This allows even quantitative discussions of localized reactivity in overstretched chain (segments) to dispense with the macromolecule and focus on the much smaller, more tractable reactive site, whose Examples of non-scissile and scissile mechanophores: the polymer-backbone contributing bonds are blue; the scissile bonds bold; red arrows show the pulling axis. Rare mechanochemically dethreadable rotaxanes [29][30] constitute a separate type of scissile mechanophores excluded here because they have been insufficiently studied. (C) Reported force-dependent activation free energies, ΔG ‡ .…”

“…(B)Examples of non-scissile and scissile mechanophores: the polymer-backbone contributing bonds are blue; the scissile bonds bold; red arrows show the pulling axis. Rare mechanochemically dethreadable rotaxanes[29][30] constitute a separate type of scissile mechanophores excluded here because they have been insufficiently studied. (C) Reported force-dependent activation free energies, ΔG ‡ .…”