The discovery of exhaustive (nearly quantitative) post-polymerization modifications (PPM) relies heavily on the efficiency of their corresponding small-molecule protocols. However, the direct translation of existing small-molecule protocols into PPM methods has never been guaranteed due to the intrinsic differences between small-molecule substrates and polymers. Herein, we introduce the direct optimization on polymers (DOP) as a complementary approach to developing exhaustive PPM reactions. As proof of the DOP concept, we present an exhaustive Baeyer-Villiger (BV) post-modification which cannot be accessed by conventional approaches. This user-friendly methodology provides general access to synthetically challenging copolymers of vinyl acetate and more activated monomers (MAMs) including both statistical and narrow-dispersed block copolymers. Furthermore, a scalable one-pot copolymerization/exhaustive BV post-modification procedure was developed to produce such materials showing improved performance over regular PVAc.
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