Exhaustive Baeyer–Villiger oxidation: a tailor-made post-polymerization modification to access challenging poly(vinyl acetate) copolymers. Issue 40 (12th September 2022)

• Record Type: Journal Article
• Authors: Ma, Pengfei; Plummer, Christopher M.; Luo, Wenjun; Pang, Jiyan; Chen, Yongming; Li, Le
• Is Part Of: Chemical science. Volume 13:Issue 40(2022)
• Page Start: 11746
• Page End: 11754
• Publication Date: 2022-09-12
• Subjects: Chemistry -- Periodicals; 540.5
• DOI: 10.1039/d2sc03492a
• Languages: English
• ISSNs: 2041-6520

Abstract

Abstract : Exhaustive Baeyer–Villiger (BV) oxidation, which was developed by a direct optimization on polymers (DOP) approach, provides a general solution for preparing synthetically challenging poly(vinyl acetate) statistical and block copolymers. Abstract : 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.