Facile Access to Functional Polymer Materials via Living Lewis Pair Polymerization and Post-Polymerization Modification

Being a versatile platform for the production of functional polymers, vinyl-containing polymers are difficult to synthesize through traditional living polymerization techniques, which typically require strict control over reaction conditions to prevent crosslinking. Herein, we employed living/controlled Lewis pair polymerization (LPP) to transform allyl methacrylate into soluble poly(allyl methacrylate) with high molecular weights (up to M_n = 1143 kg/mol) and narrow molecular weight distributions (Đ = 1.07–1.32), leaving vinyl pendants intact in every repeat unit. Well-defined block or random copolymers can be synthesized through the regulation of the position and density of the pendent vinyl sites on polymer chains. In combination with thiol–ene click reactions, different types of functional groups could be introduced to the polymeric framework, furnishing various functionalized polymers with different topologies, including photo-responsive, self-healing, or amphiphilic linear polymers, graft plastics, and cross-linked elastomers with enhanced strength and toughness. This strategy enables the preparation of vinyl-containing polymers with adjustable architectures, exhibiting promising application potentials in the synthesis of functional materials.