Design of Pyrazole-Pendant Acrylamide Monomers Enabling Selective Postpolymerization Modification for Library Synthesis of Random/Block Copolymers

We report pyrazole-substituted acrylamides as pendant-transformable monomers that enable selective postpolymerization modification (PPM) via aminolysis without the need for a catalyst. The monomers are sufficiently stable to undergo radical (co)polymerization, yet their pendant groups are readily converted to amide groups by aminolysis with alkylamines after polymerization. The aminolysis reactivity is strongly dependent on the pyrazole substituents and the solvent. By exploiting the contrasting reactivity of two pyrazole acrylamides, we achieved random (statistical) or block copolymerization, followed by selective PPM in different solvents, yielding libraries of acrylamide copolymers bearing diverse side chains. Notably, aliquots from a single “mother” copolymer prepared on scale can be divergently transformed to furnish a library of copolymers with identical primary structures (molecular weight, dispersity, and sequence) but distinct pendant groups. This approach provides a powerful platform for rigorous structure–property correlation studies and data-driven materials informatics based on copolymer libraries.