Scavenger Resin Enabling Simplification of Complicated Living Anionic Polymerization

Abstract

Since Szwarc first proposed living anionic polymerization in Nature (1956), this method has proven to be the most powerful approach for large-scale synthesis of nearly uniform polymers with tunable compositions and microstructures. Eliminating various impurities toward the absolute purification of reagents and vessels is a prerequisite for living polymerization. Conventional purification methods are laborious and highly specific for the reagents, significantly limiting the potential of the anionic polymerization. Herein, we develop a facile and universal purification method by the anionic initiating scavenger resin that eliminates impurities via self-sacrificial reactions, substantially simplifying the process. For representative synthesized homopolymers, the degree of polymerization (DP) shows a strict linear correlation with monomer/initiator molar ratios (R) according to DP = R while maintaining low dispersity indices (Đ ≈ 1.03). The living anionic polymerization also enables scalable production of nearly uniform copolymers through designed one-batch sequential polymerization. This large-scale synthesis of composition-controlled polymers with a narrow distribution advances the fundamental understanding of structure-performance relationships and supports the precise construction of uniform self-assembled nanostructures.