Mechanochemical solid-state vinyl polymerization with anionic initiator

Mechanochemistry has been extended to various polymer syntheses to achieve efficiency, greenness, and new products. However, many fundamental polymerization reactions have not been explored, although anionic polymerization of vinyl compounds has been pursued under mechanochemical conditions. Two solid monomers, 4-biphenyl methacrylate and 4-vinyl biphenyl, representing methacrylate and styrenic classes, respectively, were reacted with secondary butyl lithium under high-speed ball-milling. The alkyl-anion-promoted polymerization process was established by excluding radical initiation and producing the expected polymers with good efficiency. However, the generally expected features of anionic polymerization, such as molecular weight control and narrow dispersity, were not observed. Analysis of the milling parameters, reaction monitoring, and microstructural analysis revealed that the mechanism of the mechanochemical process differs from that of conventional anionic polymerizations. The mechanical force fractured the newly formed polymer chains via anionic initiation and generated macroradicals, which participated in the polymerization process. The anionic process governs the initiation step and the radical process becomes dominant during the propagation step.