中国科学院上海有机化学研究所洪缪研究小组揭示了具有完全可降解碳骨架的乙烯基聚合物,由芳构化驱动的C-C键裂解实现。2025年3月13日出版的《自然-化学》发表了这项成果。
在这里,该课题组研究人员报告芳香化驱动的C-C键裂解作为一种可行而有力的策略,以赋予碳骨架主题丙烯酸聚合物的可降解性为例。这个新策略的关键是丙烯酸酯与简单的、商业上可获得的和生物可再生的香豆素的高效、活性、交替加成共聚。由此产生的丙烯酸共聚物是坚固的,透明的热塑性塑料,具有与聚甲基丙烯酸甲酯相当或优于聚甲基丙烯酸甲酯的关键热,光学,机械性能。在强碱作用下,交替共聚物可以在室温下完全降解,通过主链C-C键的有效裂解,利用芳构化作为热力学驱动力,生成纯的、具有药用价值的分子,从而提供耐用、稳定且完全可降解的碳骨架丙烯酸聚合物。
研究人员表示,碳骨架聚合物构成了大多数塑料,由于其主链C-C键强而惰性,其降解仍然是一个艰巨的挑战。虽然在一定条件下加入产生主自由基的共聚单体可以引起聚合物链的降解,但这种策略会产生复杂的低聚物混合物。
附:英文原文
Title: Vinyl polymers with fully degradable carbon backbones enabled by aromatization-driven C–C bond cleavage
Author: Zhang, Zhen-Hua, Sun, Yangyang, Rajeshkumar, Thayalan, Li, Yuesheng, Maron, Laurent, Hong, Miao
Issue&Volume: 2025-03-13
Abstract: Degradation of carbon-backbone polymers, which make up most plastics, remains a formidable challenge owing to strong and inert main-chain C–C bonds. While incorporation of comonomers that generate backbone radicals under certain conditions can induce degradation of the polymer chain, such strategies yield complex oligomer mixtures. Here we report aromatization-driven C–C bond cleavage as a viable and powerful strategy to endow the degradability into carbon backbones using acrylic polymers as a model example. The key to this new strategy is the efficient, living, alternating addition copolymerization of acrylates with simple, commercially available and biorenewable coumarin using a frustrated Lewis pair cooperative catalyst. The resulting acrylic copolymers are strong, transparent thermoplastics with key thermal, optical, mechanical properties comparable or superior to poly(methyl methacrylate). Under strong base, alternating copolymers can completely degrade at room temperature through efficient cleavage of main-chain C–C bonds utilizing aromatization as a thermodynamic driving force, to generate pure, pharmaceutically valuable molecules, thus affording durable, robust yet fully degradable carbon-backbone acrylic polymers.
DOI: 10.1038/s41557-025-01751-w
Source: https://www.nature.com/articles/s41557-025-01751-w
Nature Chemistry:《自然—化学》,创刊于2009年。隶属于施普林格·自然出版集团,最新IF:24.274
官方网址:https://www.nature.com/nchem/
投稿链接:https://mts-nchem.nature.com/cgi-bin/main.plex