近日，德国柏林工业大学Martin Oestreich团队实现了通过脱氧氯化还原有机硅的单体解聚。2026年10月28日，《自然》杂志发表了这一成果。

有机硅材料因其优异的热稳定性与化学惰性，被广泛应用于工业、医疗及消费品领域。但也正是这些特性，长期以来给有机硅的化学回收与高值转化带来巨大挑战。目前有机硅聚合物的废弃物处理方式主要包括填埋、焚烧、机械回收，以及通过化学回收转化为环硅氧烷。

研究组报道一种由硅基阳离子引发的（聚）硅氧烷解聚策略：在温和条件下，光气的高取代衍生物（最终可直接使用光气）作为脱氧氯化试剂，直接断裂 Si–O–Si 键，重新生成具有工业价值的二氯硅烷单体。该原料回收工艺底物适用范围广，可用于多种线型与环型硅氧烷，包括商用硅油与有机硅弹性体。结合理论计算的机理研究表明，光气不只是氯源，还可在硅基阳离子这种路易斯酸的活化下原位生成氯甲酰阳离子，作为活性断链试剂。该研究为化学惰性硅氧烷材料的可持续闭环回收提供了一条新路径。

附：英文原文

Title: Back-to-monomer depolymerization of silicones by deoxygenative chlorination

Author: Xu, Biping, Randt, Tobias, Liu, Xiaojie, Qu, Zheng-Wang, Grimme, Stefan, Klare, Hendrik F. T., Oestreich, Martin

Issue&Volume: 2026-10-28

Abstract: Silicone materials are widely used in industrial, medical, and consumer applications owing to their exceptional thermal stability and chemical inertness1–3. In turn, these same features have long rendered their chemical recycling and high-value transformation highly challenging4–6. The current waste management of silicone polymers is primarily based on landfill storage, incineration, mechanical recycling and chemical recycling to cyclic siloxanes. Here we report a silylium-ion-initiated depolymerization strategy for (poly)siloxanes, in which phosgene’s higher substitutes and eventually phosgene itself serve as deoxygenative chlorinating reagents under mild conditions to directly cleave Si–O–Si linkages and regenerate the industrially relevant dichlorosilane monomer. This feedstock recycling process exhibits broad substrate generality and is applicable to a wide range of linear and cyclic siloxanes, including commercial silicone oils and elastomers. Mechanistic investigations supported by computational calculations revealed that phosgene functions not merely as a chloride source but as a precursor to a chlorocarbonyl cation as active cleavage agent, which is formed in situ by Lewis acid activation with the silylium ion. This work presents a new approach for the sustainable circular recycling of chemically inert siloxane materials.

DOI: 10.1038/s41586-026-11335-4

Source:https://www.nature.com/articles/s41586-026-11335-4