C-H Functionalization of Poly(ethylene oxide) - Embracing Functionality, Degradability, and Molecular Delivery.

IF 4.2 3区 化学 Q2 POLYMER SCIENCE Macromolecular Rapid Communications Pub Date : 2024-10-07 DOI:10.1002/marc.202400613
Se Jong Kim, Eun Ji Hong, Nuri Kim, Nuri Kim, Minseong Kim, Aram Shin, Byeong-Su Kim, Dong Won Lee, Jeung Gon Kim
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Abstract

This study presents an organocatalytic C-H functionalization approach for postpolymerization modification (PPM) of poly(ethylene oxide) (PEO). Most of PEO PPM is previously processed at the end hydroxy group, but recent advances in C-H functionalization open a way to modify the backbone position. Structurally diverse carboxylic acids are attached to PEO through a cascade process of radical generation by peroxide and oxidation to oxocarbenium by tertiary butylammonium iodide. Attaching carboxylic acids yields a series of functionalize PEO with acetal units (2-5 mol%) in a backbone, which is not accessible via conventional copolymerization of epoxides. The optimized conditions minimizes the uncontrolled degradation or crosslinking from the highly reactive radical and oxocarbenium intermediate. The newly introduced acetal units bring degradability of PEO as well as delivery of carboxylic acid molecules. Hydrolysis studies with high molecular weight functionalization PEO (Mn = 13.0 kg mol-1) confirm the steady release of fragmented PEO (Mn ∼ 2.0 kg mol-1) and carboxylic acid over days and the process rate is not sensitive to pH variation between pH 5 and 9. The presented method offers a versatile and efficient way to modify PEO with potential energy and medical applications.

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聚环氧乙烷的 C-H 功能化--兼具功能性、降解性和分子传递性。
本研究介绍了一种用于聚环氧乙烷(PEO)后聚合改性(PPM)的有机催化 C-H 功能化方法。大多数 PEO PPM 以前都是在末端羟基上进行加工的,但最近在 C-H 功能化方面取得的进展为改变骨架位置开辟了一条途径。通过过氧化物产生自由基和叔丁基碘化铵氧化成氧羰基的级联过程,结构各异的羧酸被连接到 PEO 上。羧酸的附着产生了一系列在骨架中含有缩醛单元(2-5 摩尔%)的官能化 PEO,而传统的环氧化物共聚是无法获得这种官能化 PEO 的。优化的条件最大程度地减少了高活性自由基和氧羰基中间体造成的不可控降解或交联。新引入的缩醛单元提高了 PEO 的降解性和羧酸分子的传递性。对高分子量官能化 PEO(Mn = 13.0 kg mol-1)进行的水解研究证实,片段化 PEO(Mn ∼ 2.0 kg mol-1)和羧酸可在数天内稳定释放,且过程速率对 pH 值 5 至 9 之间的变化不敏感。所介绍的方法为改性 PEO 提供了一种多功能、高效的途径,具有潜在的能源和医疗应用价值。
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来源期刊
Macromolecular Rapid Communications
Macromolecular Rapid Communications 工程技术-高分子科学
CiteScore
7.70
自引率
6.50%
发文量
477
审稿时长
1.4 months
期刊介绍: Macromolecular Rapid Communications publishes original research in polymer science, ranging from chemistry and physics of polymers to polymers in materials science and life sciences.
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