Synthesis of Quadruple Hydrogen-Bonded Monomers for START Terpolymerization to Prepare Main-Chain-Type Fluorinated Supramolecular Terpolymers

In this work, quadruple hydrogen bond-driven supramolecular monomer olefin-terminated ureido-pyrimidinones (UPys) are developed for START terpolymerization to prepare main-chain-type semifluorinated alternating terpolymers (SFAT-Us). The terpolymerizations are investigated in detail by a kinetic study and NMR characterization of the prepared polymers. It is notable that the molar mass of the fluorinated supramolecular terpolymers can be adjusted solely by changing the solvent due to the dynamic reversibility of the formation of quadruple hydrogen bonding. Supramolecular terpolymers with tailor-made noncovalent cross-linking densities can be achieved by controlling the feeding ratios of comonomers. Finally, fluorine-containing materials, which are able to self-heal, can be obtained by end-group modification of the as-prepared supramolecular terpolymer. Overall, this work provides a new strategy for the synthesis of fluorinated supramolecular polymers, broadening the variety of fluorinated polymers.