A New Class of Mechano-Responsive PolyureThane Via Anthracene -TAD Diels-Alder (DA) Click Chemistry

Smart or stimuli-responsive polymers have garnered significant interest in the scientific community due to their response to different stimuli like pH, temperature, light, mechanical force, etc. Mechanophoric polymer is an intriguing class of smart polymers that respond to external mechanical force by producing fluorescent moieties and can be utilized for damage detection and stress-sensing assessment. In recent reports on mechanophoric polymers, different mechanophoric motifs such as spiropyran, rhodamine, coumarin, etc. are explored. This investigation reports a new kind of mechanophoric polyurethane (PU) adduct based on Diels-Alder (DA) click chemistry. Here, an anthracene(An)-end capped tri-armed urethane system is synthesized, followed by a DA reaction using bis-(1,2,4-triazoline-3,5-dione) (bis-TAD) derivative. The incorporation of bis-TAD in the urethane system renders the anthracene inactive ("turn-off") by dismantling its conjugation as a result of a successful DA reaction. The soft PU translated into a harder material through bis-TAD linkages between polymer chains as evident from nanoindentation (NINT) analysis. The resulting material reverts back to its fluorescent "turned-on" mode owing to a force-accelerated retro-Diels-Alder (r-DA) reaction. Besides the mechanophoric attributes, the material demonstrates self-healing behavior examined by microscopic investigations. This innovative approach can be a potential route to design responsive polymers with dynamic functionalities for advanced material applications. Stimuli-responsive polymers, including mechanophoric variants, are intriguing for their unique properties and found useful for damage assessment. This study introduces a novel mechanophoric Diels-Alder polyurethane adduct employing Diels-Alder Click chemistry. Anthracene end-capped urethane undergoes a D-A reaction with a bis-TAD derivative, rendering anthracene inactive. However, mechanical force triggers a r-Diels-Alder reaction, restoring fluorescence. image