Solvent-Free Mechanochemical Post-Polymerization Modification of Ionic Polymers

Despite their superior stability and facile handling, ionic polymers have limited solubility in most organic solvents, restricting the range of substrates and reaction conditions to which they can be applied. To overcome this solubility issue, the present study presents a solvent-free mechanochemical reaction. Specifically, a post-polymerization modification of ammonium-functionalized polyether was demonstrated using a solvent-free vibrational ball-milling technique. The formation of imine bonds between the ionic polymer and an aromatic aldehyde led to the complete conversion to imine within 1 h without any bond breakage on the polymer backbone. The viability of this approach for a wide range of aldehydes was also evaluated, highlighting the potential of the mechanochemical post-polymerization modification of polymers that are inaccessible by conventional solution approaches.