Chemical recycling of mixed plastic waste can recover hydrocarbon products, but additive-derived non-intentionally added substances (NIASs) and other volatile or extractable residues may affect product quality and safety. In this study, six polyolefin-rich waste streams (P1–P6) were analyzed by analytical pyrolysis coupled with comprehensive two-dimensional gas chromatography-time-of-flight mass spectrometry (Py–GC×GC–TOF–MS), while three additional consumer-grade plastics (P7–P9) were examined by headspace/solvent-extraction GC–MS and aqueous migration testing to profile volatile organic compounds (VOCs), semi-volatile organic compounds (SVOCs), and water migrants. Under rapid pyrolysis at 650 °C, the condensable products were dominated by C5–C30 aliphatic hydrocarbons. Polyethylene (PE)-rich feeds produced mainly n-paraffins and α-olefins, whereas polypropylene (PP)-rich feeds produced more branched olefins and modest mono-aromatics. Oxygenated compounds were negligible in non-oxidized feeds, but persisted at low levels in weathered high-density polyethylene (HDPE), consistent with pre-existing oxidation. Antioxidant-derived NIASs, including 2,4-di-tert-butylphenol and an Irganox 1010-related spiro-dione, were detected at trace to low area-fraction levels. VOC/SVOC and migration analyses revealed mainly low-intensity hydrocarbons, esters, antioxidant-related degradation products, caprolactam, and selected plasticizer-related compounds. These results show that relatively clean polyolefin streams can yield hydrocarbon-rich pyrolysates, but oxidized PE and additive-derived NIASs remain important quality-control targets. The GC-based methods used here characterize the volatile, condensable, and readily extractable fraction and do not represent the total contaminant load of the source waste.
Chen et al. (Tue,) studied this question.