印度国家化学实验室（CSIR）Nagaraju Barsu团队报道了钌催化聚烯烃解构：一种将废聚乙烯回收为高附加值烯烃的策略。相关研究成果于2025年1月22日发表在国际顶尖学术期刊《德国应用化学》。

从消费后的废聚烯烃合成增值产品既有趣又具有挑战性。

该文中，研究人员报道了钌催化聚乙烯上循环生成长链烯烃衍生物。开发的方法主要涉及两个步骤，即通过氢原子转移使聚乙烯脱氢，以及使用HG-II催化剂进行复分解。使用钌催化聚乙烯脱氢得到高达3.38%的双键；其中90%为回收的聚烯烃材料。使用HG-II催化体系将获得的不饱和聚乙烯与乙烯进行交叉复分解。这导致了主要十二烯（C12）衍生物的合成，选择性为58%，以及不同链长的其他衍生物。整个反应分别以1:0.8的比例产生末端烯烃和内烯烃。通过核磁共振波谱、凝胶渗透色谱（GPC）和差示扫描量热法（DSC）证实了聚乙烯的脱氢及其解构。C12选择性的起源已通过对照实验得到证实。

该方法的范围扩大到消费后的废聚乙烯，作为主要产品，其增值十二烯衍生物的转化率很高。

附：英文原文

Title: Ruthenium-Catalyzed Deconstruction of Polyolefins: A Strategy to Up-cycle the Waste Polyethylene to Value-Added Alkenes

Author: Nagaraju Barsu, Ganeshdev Padhi, Kishor V. Khopade, Nageswararao Moyilla, Raghavendrakumar Rangappa, Samir H. Chikkali

Issue&Volume: 2025-01-22

Abstract: Synthesis of value-added products from post-consumer waste polyolefins is fascinating as well as challenging. Here we report ruthenium-catalyzed up-cycling of the polyethylene to long-chain alkene derivatives. The developed methodology mainly involves two steps i.e., dehydrogenation of polyethylene through hydrogen atom transfer and its metathesis using the HG-II catalyst. The dehydrogenation of polyethylene using ruthenium catalysis derived up to 3.38%, of double bonds; with 90% of the recovered polyolefin material. The obtained unsaturated polyethylene was subjected to cross-metathesis with ethylene using HG-II catalytic system.  This resulted in the synthesis of predominantly dodecene (C12) derivatives, with 58% selectivity, along with other derivatives of varying chain lengths. The overall reaction produced terminal and internal olefins in the ratio 1:0.8 respectively.  The dehydrogenation of polyethylene and its deconstruction was confirmed by NMR spectroscopy, Gel Permeation Chromatography (GPC) and Differential Scanning Calorimetry (DSC). The origin of C12 selectivity has been demonstrated by control experiments. The scope of the methodology was extended to post-consumer waste polyethylene gave high conversion of value-added dodecene derivatives as a major product.

DOI: 10.1002/anie.202422609

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202422609