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彻底的拜耳-维利格氧化反应：一种定制的后聚合修饰方法，用于制备具有挑战性的聚醋酸乙烯酯共聚物。

Exhaustive Baeyer-Villiger oxidation: a tailor-made post-polymerization modification to access challenging poly(vinyl acetate) copolymers.

作者信息

Ma Pengfei, Plummer Christopher M, Luo Wenjun, Pang Jiyan, Chen Yongming, Li Le

机构信息

School of Chemistry, Sun Yat-sen University Guangzhou 510275 P. R. China

Key Laboratory for Polymeric Composite and Functional Materials of Ministry of Education, Sun Yat-sen University Guangzhou 510275 P. R. China.

出版信息

Chem Sci. 2022 Sep 6;13(40):11746-11754. doi: 10.1039/d2sc03492a. eCollection 2022 Oct 19.

DOI:10.1039/d2sc03492a
PMID:36320906
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC9580620/
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.

摘要

彻底（近乎定量）的聚合后修饰（PPM）的发现很大程度上依赖于其相应小分子方案的效率。然而，由于小分子底物和聚合物之间的内在差异，现有小分子方案直接转化为PPM方法从未得到保证。在此，我们引入聚合物直接优化（DOP）作为开发彻底PPM反应的一种补充方法。作为DOP概念的证明，我们展示了一种传统方法无法实现的彻底的拜耳-维利格（BV）后修饰。这种用户友好的方法为合成具有挑战性的醋酸乙烯酯与更多活性单体（MAM）的共聚物提供了通用途径，包括无规和窄分布嵌段共聚物。此外，还开发了一种可扩展的一锅法共聚/彻底BV后修饰程序来制备此类材料，其性能优于常规聚醋酸乙烯酯（PVAc）。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/a355/9580620/f13512c74604/d2sc03492a-f7.jpg
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https://cdn.ncbi.nlm.nih.gov/pmc/blobs/a355/9580620/f13512c74604/d2sc03492a-f7.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/a355/9580620/e97a4dea4a40/d2sc03492a-s1.jpg
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