Nitroarene Photoactivation Promotes Oxidative Deconstruction of Olefinic Polymers.

IF 5.1 Q1 POLYMER SCIENCE

ACS Macro Letters Pub Date : 2025-07-01 DOI:10.1021/acsmacrolett.5c00329

Thi H Le,Kamal Bhatt,Sylwia Dworakowska,Kevin A Stewart,Parker T Boeck,Adam S Veige,Daniel Seidel,Brent S Sumerlin

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Abstract

Photoactivation of nitroarenes has been recently reported to induce the transformation of alkenyl bonds into carbonyl functionalities. Capitalizing on this unique photochemical mechanism, this study explores the use of nitroarenes to achieve oxidative cleavage of olefinic polymers under visible light irradiation. The degradation of various olefinic polymers, including commercially available polybutadiene, polynorbornene, both linear and cyclic poly(phenylacetylene), as well as backbone-modified polyacrylates with alkenyl functionality was investigated. To elucidate the efficacy of this methodology, a series of nitroarene derivatives bearing variable substituents were screened for their degradative efficiency on polybutadiene. Varying nitroarene stoichiometry, reaction temperature, and pos-treaction workup conditions were investigated to optimize degradation conditions. The results demonstrated that photoexcited nitroarenes enable efficient oxidative degradation of olefinic polymers in a safe and sustainable manner, providing a novel strategy for mild macromolecular deconstruction.

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硝基芳烃光活化促进烯烃聚合物的氧化解构。

最近有报道称，硝基芳烃的光活化可诱导烯基键转变为羰基官能团。利用这种独特的光化学机制，本研究探索了在可见光照射下使用硝基芳烃实现烯烃聚合物的氧化裂解。研究了各种烯烃聚合物的降解，包括市售的聚丁二烯、聚降冰片烯、线性和环状聚苯乙炔以及具有烯基官能团的骨架改性聚丙烯酸酯。为了验证该方法的有效性，筛选了一系列具有可变取代基的硝基芳烃衍生物对聚丁二烯的降解效率。研究了不同的硝基芳烃化学计量、反应温度和反应后的处理条件，以优化降解条件。结果表明，光激发硝基芳烃能够以安全和可持续的方式高效氧化降解烯烃聚合物，为温和的大分子解构提供了一种新的策略。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

ACS Macro Letters 化学-

CiteScore

10.40

自引率

3.40%

发文量

209

审稿时长

1 months

期刊介绍： ACS Macro Letters publishes research in all areas of contemporary soft matter science in which macromolecules play a key role, including nanotechnology, self-assembly, supramolecular chemistry, biomaterials, energy generation and storage, and renewable/sustainable materials. Submissions to ACS Macro Letters should justify clearly the rapid disclosure of the key elements of the study. The scope of the journal includes high-impact research of broad interest in all areas of polymer science and engineering, including cross-disciplinary research that interfaces with polymer science. With the launch of ACS Macro Letters, all Communications that were formerly published in Macromolecules and Biomacromolecules will be published as Letters in ACS Macro Letters.