Mechanochemical Polymerization Not Limited By Miscibility

Mechanochemistry has emerged as a powerful and indispensable paradigm in synthetic chemistry. In the field of polymer science, its application has rapidly evolved beyond conventional chain degradation, firmly establishing its viability in fundamental polymerization pathways including radical, ionic, and coordination polymerizations. Moving forward from merely translating established solution-phase reactions to the solid state, mechanochemistry now paves the way toward the architectural design of "new-to-the-world" polymers via completely innovative processes. Over the past decade, our research group has intensely focused on mechanochemical polymer synthesis. Through these endeavors, we have demonstrated that solid-state polymerization can effectively transcend the critical limitations of solution-phase chemistry, particularly when confronting severe challenges related to solubility and monomer miscibility. In this presentation, we introduce our recent fundamental investigations tracing the blending and mass-transport phenomena of distinct chemical species within a ball mill. Building upon these insights, we demonstrate unprecedented polymerization cases utilizing monomer combinations that defy traditional thermodynamic mixing rules. Ultimately, this work highlights that mechanochemical synthesis is not just an alternative protocol, but a pivotal vehicle that significantly expands the boundaries and capabilities of modern polymer chemistry.