Ruthenium‐Catalyzed Deconstruction of Polyolefins: A Strategy to Up‐cycle Waste Polyethylene to Value‐Added Alkene

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 which gave high conversion to value‐added dodecene derivatives as a major product.