The development of a multicolor mechanochromic polymer/silica composite is achieved by using two distinct types of mechanochromophores. The multicolor mechanochromism of the composite containing diarylbibenzofuranone in silica-rich domains and naphthopyran in the polymer-rich domain is observed. The obtained composite shows blue, green, and orange colors according to the intensity of applied mechanical stimuli, solvent addition, and lapse of time. This unique multicolor mechanochromic behavior is evaluated by solid-state UV–vis absorption spectroscopy, ab initio steered molecular dynamics simulations, and computed minimum energy paths on force-modified potential energy surfaces. The unique mechanochromism is attributed to the difference in properties, activated colors, and domain locations between the two mechanochromophores.

Mechanochromism, a color change induced by mechanical force, has attracted much attention in materials science, as it can be used to create stress- and damage-detecting sensors. In particular, radical-type mechanochromic molecules (mechanochromophores), which produce colored radicals upon exposure to mechanical force, enable the qualitative visualization of mechanical stress and the quantitative evaluation of the generated radical species by electron paramagnetic resonance spectroscopy. However, the sensitivity of radical-type mechanochromophores to thermal stimuli limits their range of applications. Herein, we report the radical-type mechanochromophore difluorenylsuccinonitrile (DFSN), which can be used to synthesize mechanochromic polymers via living radical polymerization techniques, as its central carbon–carbon bond exhibits high thermal stability. The obtained DFSN-centered polymers show mechanochromism and desirably high thermal resistance.

Macromolecular rotaxane cross-linkers having two radically polymerizable vinyl groups (RCs) were first synthesized and used to prepare network polymers. A crown ether/sec-ammonium-type pseudorotaxane initiator having an OH terminal-containing axle and a crown ether wheel with a vinyl group was subjected to the living ring-opening polymerization of δ-valerolactone followed by end-capping with a bulky isocyanate to yield a polyester axle-tethering macromolecular [2]­rotaxane cross-linker (RC). Rotaxane cross-linked polymers (RCPs) were prepared by the radical polymerization of n-butyl acrylate in the presence of RCs (0.25, 0.50 mol %). The properties of the RCPs and covalently cross-linked polymers (CCPs) were characterized mainly by mechanical properties. Both fracture stress and strain values of RCPs were much higher than those of CCPs, probably owing to the increased network homogeneity by the rotaxane cross-link. The hybrid-type RCPs obtained from a mixture of RC and covalently connected cross-linker (CC) showed poorer mechanical properties similar to that of CCPs, indicating the importance of RCs in increasing the toughness of the network polymers.

Mechanochromic polymers, that is, polymers sensitive to mechanical impact, promise great potential for applications in damage sensors. In particular, radical-type mechanochromic polymers, which produce colored radical species in response to mechanical stress, may enable not only the visualization of mechanical stress, but also its quantitative evaluation by electron paramagnetic resonance analysis. Herein, a radical-type mechanochromic polymer that exhibits a color change from white to green upon dissociation of a diarylbibenzothiophenonyl moiety at the mid-point of a polystyrene chain is presented, and its mechanochromic behavior is examined. Mechanochromic materials that show a variety of colors ("rainbow colors") in response to mechanical stress were prepared by simply mixing radical-type mechanochromic polymers of primary colors.

A difluorenylsuccinonitrile-(DFSN)-based linker, whose central C−C bond is readily cleaved under mechanical stress to generate a relatively stable pink radical species, was introduced into polymer networks. DFSN-based cross-linked polymers exhibit improved mechanical properties as compared to those of the corresponding covalently cross-linked polymers owing to the energy dissipation induced by cleavage of the central DFSN bond. The toughening mechanism of DFSN-based elastomers is qualitatively visualized by the intensity of the pink color and can be quantitatively characterized by electron paramagnetic resonance. These results demonstrate that the extent of DFSN cleavage is the main factor improving the mechanical properties of the polymer networks.