近日，上海交通大学唐山及其研究小组通过机械化学骨干编辑开发出可控降解的乙烯基聚合物。2024年5月27日，国际知名学术期刊《德国应用化学》发表了这一成果。

据悉，完全饱和烃骨干的化学惰性性质赋予了乙烯基聚合物理想的耐久性，但也导致了它们显著的环境持久性。提高这些材料的可持续性需要一个关键但具有挑战性的转变——将惰性骨干转化为可降解的骨干。

该研究团队提出了一个通用的机械化学平台，通过光干扰可逆加成-破碎链转移(RAFT)共聚，将环丁烯并琥珀酰亚胺(CBS)单元沿骨干整合，将乙烯基聚合物的完全饱和骨干编辑成可降解的聚合物链。值得注意的是，均匀插入的CBS单元不会影响热稳定性或化学稳定性，而是提供了一种调整聚甲基丙烯酸酯(PMA)性能的方法。

同时，根据需要，可以通过机械化学活化(脉冲超声或球磨)选择性地将反应性无环亚胺单元引入骨干。随后无环亚胺基团的水解实现有效降解，产生远链低聚物。这种方法有望通过骨干编辑激发更环保的乙烯基聚合物的设计和修改。

附：英文原文

Title: Mechanochemical Backbone Editing for Controlled Degradation of Vinyl Polymers

Author: Zhuang Li, Xiaohui Zhang, Yajun Zhao, Shan Tang

Issue&Volume: 2024-05-27

Abstract: The chemically inert nature of fully saturated hydrocarbon backbones endows vinyl polymers with desirable durability, but it also leads to their significant environmental persistence. Enhancing the sustainability of these materials requires a pivotal yet challenging shift: transforming the inert backbone into one that is degradable. Here, we present a versatile platform for mechanochemically editing the fully saturated backbone of vinyl polymers towards degradable polymer chains by integrating cyclobutene-fused succinimide (CBS) units along backbone through photo-iniferter reversible addition-fragmentation chain-transfer (RAFT) copolymerization. Significantly, the evenly insertion of CBS units does not compromise thermal or chemical stability but rather offers a means to adjust the properties of polymethylacrylate (PMA). Meanwhile, reactive acyclic imide units can be selectively introduced to the backbone through mechanochemical activation (pulse ultrasonication or ball-milling grinding) when required. Subsequent hydrolysis of the acyclic imide groups enables efficient degradation, yielding telechelic oligomers. This approach holds promise for inspiring the design and modification of more environmentally friendly vinyl polymers through backbone editing.

DOI: 10.1002/anie.202408225

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202408225