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Using waste poly(vinyl chloride) to synthesize chloroarenes by plasticizer-mediated electro(de)chlorination


New approaches are needed to both reduce and reuse plastic waste. In this context, poly(vinyl chloride) (PVC) is an appealing target as it is the least recycled high-production-volume polymer due to its facile release of plasticizers and corrosive HCl gas. Herein, these limitations become advantageous in a paired-electrolysis reaction in which HCl is intentionally generated from PVC to chlorinate arenes in an air- and moisture-tolerant process that is mediated by the plasticizer. The reaction proceeds efficiently with other plastic waste present and a commercial plasticized PVC product (laboratory tubing) can be used directly. A simplified life-cycle assessment reveals that using PVC waste as the chlorine source in the paired-electrolysis reaction has a lower global warming potential than HCl. Overall, this method should inspire other strategies for repurposing waste PVC and related polymers using electrosynthetic reactions, including those that take advantage of existing polymer additives.

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Fig. 1: Paired-electrolysis reaction.
Fig. 2: Electroanalytical data.
Fig. 3: Structural information for PVC47k and dPVCDMP.
Fig. 4: Proposed redox-mediated paired-electrolysis mechanism.
Fig. 5: Evaluating real plastics in the paired-electrolysis reaction.

Data availability

A detailed description of the materials, equipment and methods are provided in the Supplementary Information. Furthermore, the Supplementary Information contains full characterization data for small molecules and polymers, electrochemical data, reaction screening results, LCA results and all of the other data collected in this work. When possible, all of the original data are included. In some cases, several hundred raw data files were generated for a single plot, and therefore these results are instead summarized in the tables and figures within the manuscript and its Supplementary Information. Due to the large number of raw data files, they are available from the corresponding author on reasonable request.


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We gratefully acknowledge financial support from the Howard Hughes Medical Institute Professors Program (grant no. 52008144 to A. J. M. to support D. E. F.), the Joint Center for Energy Storage Research (JCESR), a Department of Energy, Energy Innovation Hub (to A. J. M. to support D. K.), and the Agencia Nacional de Investigación e Innovación (ANII) and the Fulbright Commission in Uruguay (to S.I.C.).

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Authors and Affiliations



D.E.F. and A.J.M. conceptualized the research. D.E.F. performed all electrosynthetic experiments, data analysis, created the figures and wrote the original draft. D.K. performed all electroanalytical experiments, contributed to figure creation, data analysis and editing of the paper. The LCA was performed by S.I.C. and J.F.A. A.J.M. also contributed to the funding acquisition, data analysis, supervision and editing of the manuscript. The funders had no role in study design, data collection and analysis, the decision to publish nor the preparation of the manuscript.

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Correspondence to Anne J. McNeil.

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Nature Chemistry thanks Gary Leeke, Fu-Rong Xiu and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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A detailed description of the materials, equipment, synthetic methods, as well as all processed data generated in this study.

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Fagnani, D.E., Kim, D., Camarero, S.I. et al. Using waste poly(vinyl chloride) to synthesize chloroarenes by plasticizer-mediated electro(de)chlorination. Nat. Chem. 15, 222–229 (2023).

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