Mechanochemical Reactivity of Bottlebrush and Dendronized Polymers: Solid vs. Solution States

We explored the mechanochemical degradation of bottlebrush and dendronized polymers in solution (with ultrasonication, US) and solid states (with ball‐mill grinding, BMG). Over 50 polymers were prepared with varying backbone length and arm architecture, composition, and size. With US, we found that bottlebrush and dendronized polymers exhibited consistent backbone scission behavior, which was related to their elongated conformations in solution. Considerably different behavior was observed with BMG, as arm architecture and composition had a significant impact on backbone scission rates. Arm scission was also observed for bottlebrush polymers in both solution and solid states, but only in the solid state for dendronized polymers. Motivated by these results, multi‐mechanophore polymers with bottlebrush and dendronized polymer architectures were prepared and their reactivity was compared. Although dendronized polymers showed slower arm‐scission, the selectivity for mechanophore activation was much higher. Overall, these results have important implications to the development of new mechanoresponsive materials. The mechanochemical degradation of bottlebrush and dendronized polymers with ultrasonication (solution state) and ball‐mill grinding (solid state) was explored. This study provides important insight into the influence of polymer architecture on mechanochemical reactions and the difference in reactivity that is observed in solution and solid states, which has important implications in the development of new mechanoresponsive materials.