Mechanochromic elastomers with different thermo- and mechano-responsive radical-type mechanophores

Abstract

To design tough soft materials, the introduction of sacrificial bonds into their skeleton is a useful method. The introduction of radical-type mechanophores (RMs), which generate coloured radicals in response to mechanical stimuli, as sacrificial bonds into the cross-linking points of elastomers is expected to be a powerful tool to elucidate the fracture mechanisms as well as the toughening of materials, given that the radicals generated from the RMs are coloured and can be quantitatively evaluated using electron paramagnetic resonance (EPR) measurements. In this study, to investigate the effect of the dynamic nature, i.e., the reactivity, of RMs introduced at the cross-linking points of polymer networks on their macroscopic mechanical properties, polymer networks cross-linked by two different RMs, a symmetric radical-type mechanophore (DFSN) and a non-symmetric radical-type mechanophore (CF/ABF), were synthesized and characterized. Compared to the polymer network cross-linked by DFSN, the network with CF/ABF exhibited higher thermal and mechanical responses, in other words much more sensitive to heat and mechanical force, resulting in better stress relaxation and energy-dissipation properties. These results demonstrate that the reactivity of the radical mechanophore at the cross-linking point is an important factor for designing polymer networks.