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Mechanophores with a Reversible Radical System and Freezing‐Induced Mechanochemistry in Polymer Solutions and Gels
Authors:Dr Keiichi Imato  Atsushi Irie  Takahiro Kosuge  Dr Tomoyuki Ohishi  Dr Masamichi Nishihara  Prof Atsushi Takahara  Prof Hideyuki Otsuka
Institution:1. Department of Organic and Polymeric Materials, Tokyo Institute of Technology, 2‐12‐1 Ookayama, Meguro‐ku, Tokyo 152‐8550 (Japan);2. Graduate School of Engineering, Kyushu University, 744 Motooka, Nishi‐ku, Fukuoka 819‐0395 (Japan);3. Institute for Materials Chemistry and Engineering, Kyushu University, 744 Motooka, Nishi‐ku, Fukuoka 819‐0395 (Japan)
Abstract:Visualization and quantitative evaluation of covalent bond scission in polymeric materials are highly important for understanding failure, fatigue, and deterioration mechanisms and improving the lifetime, durability, toughness, and reliability of the materials. The diarylbibenzofuranone‐based mechanophore radical system enabled, through electron paramagnetic resonance spectroscopy, in situ quantitative evaluation of scission of the mechanophores and estimation of mechanical energy induced along polymer chains by external forces. The coagulation of polymer solutions by freezing probably generated force but did not cleave the mechanophores. On the other hand, cross‐linking led to efficient propagation of the force of more than 80 kJ mol?1 to some mechanophores, resulting their cleavage and generation of colored stable radicals. This mechanoprobe concept has the potential to elucidate other debated issues in the polymer field as well.
Keywords:cross‐linked polymers  dynamic covalent chemistry  gels  mechanochemistry  mechanochromism
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