This focused review provides an overview of our recent work and related research regarding the precise anionic ring-opening polymerization (AROP) of substituted epoxides, including alkylene oxides, glycidyl ethers, and glycidyl amines, using t-Bu-P4 as the phosphazene base catalyst to produce functional polyethers, such as homopolymers, block copolymers (BCPs), and topologically unique polymers. First, the fundamental aspects and applicable monomer scope of the t-Bu-P4-catalyzed AROP are discussed. Subsequently, the applications of the AROP system for synthesizing functional materials and architectural polymers are presented.
