Assembly and disassembly of supramolecular polymers with tunable ionic bonds

The substantial energy required to break C-C bonds (ca. 350 kJ/mol) poses challenges in conventional covalent polymer manufacturing, particularly in terms of reprocessability and recyclability. The development of supramolecular chemistry suggested an alternative way to construct multicomponent polymers based on non-covalent association of oligomer “stickers”. We demonstrate that leveraging the electrostatic interactions between chain-end(s) functionalized oligomers, supramolecular polymers can be “synthesized during use”. The chain conformation and self-assembly of these ionic supramolecular block copolymers are governed by two key factors: (1) the effective bond energy between ionic building blocks, ranging from ca. 2.5 to 250 kJ/mol, depending on end-group chemistry and dielectric properties of the polymer matrix, and (2) potential chain repulsion between dissimilar polymer chains. Notably, the effective bond energy can be readily adjusted by temperature, adding external ionic species, and external stimuli. By fine-tuning these ionic interactions, we exert control over the assembly and disassembly of ionic supramolecular block copolymers, facilitating potential phase transitions and unlocking the reprocessability and recyclability of polymeric materials.