Facile Approach to Synthesis of Ionic Polymers and Copolymerization of Immiscible Monomers Using Ball-milling
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The synthesis of ionic polymers, which can be applied to various fields such as batteries, drug delivery, hydrogels, and ion filters, has been realized under a solid-state mechanochemical ball-milling manner, promoting an eco-friendly and straightforward synthetic process. The conventional solution polymerization of ionic monomers has suffered a narrow choice of solvents and poor efficiency; direct ball-milling polymerization is not limited by solubility and miscibility. This work includes free-radical polymerization of styrene and (meth)acrylic ionic monomers and Ru-initiated ring-opening metathesis polymerization of norbornenyl ionic monomers, proving the excellent performance of mechanochemistry producing desired product polymers under the ball milling from a wide range of ionic monomers. Further exploration was accomplished with mechanochemical copolymerization of immiscible monomer pairs (ionic/hydrophobic) including sodium acetate/pyrene and sulfobetaine/porphyrin moiety. This approach facilitates the production of ionic polymers without purifications in a short time.