Mechanistic insights into the pyrolysis of poly (vinyl chloride)

Papanikolaou, Konstantinos G.; Wu, Jiayang; Huber, George W.; Mavrikakis, Manos

doi:10.1007/s10965-023-03439-6

Title: Mechanistic insights into the pyrolysis of poly (vinyl chloride)

Journal Article · Wed Jan 25 00:00:00 EST 2023 · Journal of Polymer Research

DOI:https://doi.org/10.1007/s10965-023-03439-6· OSTI ID:1922208

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Univ. of Wisconsin-Madison, WI (United States)

The accumulation of unmanaged plastic waste in the environment has a devastating impact upon marine life and human health. Catalytic and thermal pyrolysis are promising technologies toward the efficient utilization of plastic waste. Yet, the processing of polymers, such as polyvinyl chloride (PVC), that decompose into corrosive compounds remains a major challenge. In this work, we employ density functional theory (DFT) and thermogravimetric analysis (TGA) to explore the elementary chemical steps that underpin the thermal decomposition of PVC. We determine that the dehydrochlorination reaction (i.e., 1^st stage of thermal decomposition) begins in tertiary chloride defects and propagates via HCl–mediated autocatalysis of internal allylic (IA) chloride groups. The latter groups, when in the vicinity of π–conjugated polymer segments, release HCl in a facile manner. We predict that other compounds, including hydrogen halides and H₂O could also catalyze PVC’s dehydrochlorination. We suggest that hydrogen halides are the most efficient catalysts for this process, while other compounds like H₂O may slow down the dehydrochlorination compared to purely HCl-catalyzed process, because of the dilution of the produced HCl. This result is corroborated by TGA experiments. Additionally, we study the thermochemistry and kinetics of polyene chain crosslinking and the formation of aromatics. The former reaction proceeds in parallel with the dehydrochlorination process (i.e., during the 1st stage of thermal decomposition), whilst the latter may occur at high temperatures (i.e., during the 2^nd stage of thermal decomposition). Furthermore, this work contributes to the fundamental understanding of molecular scale phenomena that take place during PVC pyrolysis.

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Research Organization:: Univ. of Wisconsin-Madison, WI (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Bioenergy Technologies Office

Grant/Contract Number:: EE0009285; AC02-05CH11231

OSTI ID:: 1922208

Alternate ID(s):: OSTI ID: 1922209

Journal Information:: Journal of Polymer Research, Vol. 30, Issue 2; ISSN 1022-9760

Publisher:: Springer NatureCopyright Statement

Country of Publication:: United States

Language:: English

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Title: Mechanistic insights into the pyrolysis of poly (vinyl chloride)

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