The development of mechanochromic molecules has opened new pathways for the study of localized stress and failure in polymers. Their application as stress or temperature diagnostics, however, requires suitable measurement techniques capable of detecting the force- and temperature-sensitive chemical species with high spatial resolution. Confocal imaging techniques offer excellent spatial resolution but the energy input during these measurements can itself affect the activation state of the mechanochromic species. Here, we present a systematic study of the effects of laser-based imaging on the activation and fluorescence behavior of mechanochromic spiropyran (SP) integrated into poly(methyl acrylate) (PMA) and poly(methyl methacrylate) matrices using a confocal Raman microspectrometer. Localized stress and temperature activation were studied by means of high-rate compressive loading and dynamic fracture. Laser illumination of SP in PMA revealed a strong excitation wavelength- and power-dependence. Suitable correction functions were established and used to account for the observed laser effects. The presented study demonstrates that confocal imaging using conventional Raman spectrometers is a powerful characterization tool for localized stress analysis in mechanochromic polymers, offering quantifiable information on the activation state with high spatial resolution. However, laser-mechanophore interactions must be well understood and effects of laser excitation and exposure times must be taken into consideration when interpreting the obtained results.

Triazine-based unimolecular initiators are shown to mediate the controlled radical polymerization of several monomer classes, yielding polymers with low dispersities, targeted molecular weights, and active chain ends. We report the modular synthesis of structurally and electronically diverse triazine-based unimolecular initiators and demonstrate their ability to efficiently control the radical polymerization of modified styrene monomers. Copolymerizations of styrene with butyl acrylate or methyl methacrylate were conducted to highlight the monomer family tolerance of this system. Notably, in the case of methyl methacrylate and styrene, up to 90 mol% methyl methacrylate comonomer loadings could be achieved while maintaining a controlled polymerization, allowing the synthesis of a range of block copolymers. This class of triazine-based mediators has the potential to complement current methods of controlled radical polymerization and marks an important milestone in ongoing efforts to develop initiators and mediators with high monomer tolerance that are both metal and sulfur-free.