Full and partial amidation of poly(methyl acrylate) as basis for functional polyacrylamide (co)polymers

The direct modification of poly(methyl acrylate) (PMA) to obtain functional poly(acrylate ester)s or poly(N-alkyl acrylamide)s is generally considered to be an inefficient approach. Only in recent years, several research groups reported the possibility of the direct modification of unactivated poly(acrylate ester)s in order to obtain functional structures. Within this contribution, we explored the amidation kinetics of PMA with five different amines, utilizing triazabicyclodecene (TBD) as an organocatalyst. We demonstrate that the reaction conditions can be tuned to provide kinetic control over the functionalization degree of the polymer. The reaction kinetics revealed that amine nucleophilicity plays a larger role at the initial stages of the reaction, while steric factors and polymer solvation dominate the reaction kinetics at later stages. Finally, we demonstrate the utility of the developed approach to synthesize functional polymers with olefin side chains, which were subsequently crosslinked via thiol-ene and Alder-ene chemistry