美国普渡大学窦乐添团队研究了可回收聚二烯衍生物熔融态光诱导本体聚合策略。2025年5月28日出版的《自然-化学》杂志发表了这项成果。

聚丁二烯，特别是1,3-丁二烯衍生物，因其广泛的应用而成为化学工业不可或缺的组成部分。然而，目前的商业生产方法在很大程度上依赖于气相或溶液相工艺，涉及复杂的引发剂、催化剂和添加剂，需要额外的纯化和成本。

研究组介绍了一种超清洁的光熔体本体聚合策略，该策略能够精确合成高分子量的聚二烯，而不需要溶剂、催化剂或引发剂。使用紫外线照射，他们可以在粘液酸盐衍生物中产生长寿命的双自由基，促进受控的链传播，并使终止最少。这种方法还简化了ABA三嵌段共聚物的合成，并允许有效的无规共聚，从而产生具有优异机械性能和加工性能的塑料。 

此外，这些聚合物中固有的较弱的碳-碳键实现了以高产率轻松解聚成单体，为化学回收提供了一条有效的途径。这项工作强调了一种简单而有效的聚合方法，该方法符合绿色化学的原理，并推动了可回收聚合物材料的发展。

附：英文原文

Title: Photoinduced bulk polymerization strategy in melt state for recyclable polydiene derivatives

Author: Wu, Pengfei, Hu, Qixuan, Marquardt, Andrew V., Ogunfowora, Lawal A., Kim, Jeong Hui, Tang, Yuanhao, Lin, Chenjian, Savoie, Brett M., Dou, Letian

Issue&Volume: 2025-05-28

Abstract: Polydienes, particularly 1,3-butadiene derivatives, are integral to the chemical industry due to their widespread applications. However, current commercial production methods depend largely on gas- or solution-phase processes involving sophisticated initiators, catalysts and additives that require additional purification and cost. Here we introduce an ultraclean photo-melt-bulk polymerization strategy that enables the precise synthesis of high-molecular-weight polydienes without the need for solvents, catalysts or initiators. Using UV irradiation, we can generate long-lived biradicals in muconate derivatives that facilitate controlled chain propagation with minimal termination. This approach also simplifies the synthesis of ABA triblock co-polymers and allows for efficient random co-polymerization, yielding a plastic with excellent mechanical properties and processability. Furthermore, the inherently weaker carbon–carbon bonds in these polymers allow for facile depolymerization into monomers with high yields, providing an efficient pathway for chemical recycling. This work highlights a simple, yet effective polymerization method that aligns with the principles of green chemistry and advances the development of recyclable polymeric materials.

DOI: 10.1038/s41557-025-01821-z

Source: https://www.nature.com/articles/s41557-025-01821-z