{
  "abstract": "Post-polymerization vicinal chlorination of unsaturated polyolefins provides access to linear poly(ethylene-co-1,2-dichloroethylene) polymers that are inaccessible through conventional polymerization or post-polymerization routes. Herein, Cl 2 (g), generated in situ from N-chlorosuccinimide (NCS) and hydrochloric acid (HCl), was used to selectively convert alkene sites in polycyclooctene (PCOE)-derived polyolefins into vicinal chloride subunits. Partial hydrogenation of PCOE afforded substrates containing 4–25 mol% residual C=C, which upon chlorination, yielded polymers with controlled levels and distributions of vicinal chlorides along a linear polyethylene backbone. Incorporation of chlorides into the PCOE-derived polymers disrupts crystal formation and reduces the glass transition and melting temperatures. For the 25 mol% vicinal chloride, the polymer affords precise placement of chlorides along the polymer backbone and transforms the orthorhombic crystal structure, typical of polyethylene (PE), to a triclinic crystal structure, suggesting the incorporation of Cl atoms to the crystallites. This method was further extended to dehydrogenated post-consumer HDPE from milk jugs, affording vicinal chlorinated polyethylene containing ~ 1.1 mol% vicinal Cl, while maintaining the original polymer chain architecture and molecular weight. These results establish vicinal chlorination of unsaturated PE as a strategy for tuning polymer properties and provide a platform for upcycling PEs into value-added functional materials.",
  "abstract_shown": true,
  "affiliations": [
    "Department of Chemistry, Roy and Diana Vagelos Laboratories",
    "University of Pennsylvania",
    "Department of Chemical and Biomolecular Engineering",
    "Department of Materials Science and Engineering"
  ],
  "article_type": null,
  "arxiv": null,
  "author_total": 8,
  "authors": [
    {
      "affs": [
        0,
        1
      ],
      "name": "Pedro M. Jimenez Antenucci",
      "orcid": "0000-0001-8660-761X"
    },
    {
      "affs": [
        2,
        1
      ],
      "name": "Tingfeng Chen"
    },
    {
      "affs": [
        2,
        1
      ],
      "name": "Hoda Shokrollahzadeh Behbahani"
    },
    {
      "affs": [
        0,
        1
      ],
      "name": "Huapei Qiu"
    },
    {
      "affs": [
        0,
        1
      ],
      "name": "Lucia Lavelle"
    },
    {
      "affs": [
        0,
        1
      ],
      "name": "Emily Sidlow"
    },
    {
      "affs": [
        2,
        1,
        3
      ],
      "name": "Karen I. Winey"
    },
    {
      "affs": [
        0,
        1
      ],
      "name": "Marisa C. Kozlowski"
    }
  ],
  "bibtex": "https://research.draconitic.com/paper/8fzzt0pqvagpf.bib",
  "cited_by": 0,
  "doi": "10.26434/chemrxiv.15008874/v1",
  "fulltext_url": null,
  "id": "8fzzt0pqvagpf",
  "issns": [],
  "landing_url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008874/v1",
  "language": null,
  "licence": "CC-BY",
  "licence_label": "CC BY",
  "licence_source": "journal",
  "licence_url": "https://creativecommons.org/licenses/by/4.0/",
  "metadata_licence": null,
  "native_subjects": [
    [
      "openalex",
      "2507|Polymer crystallization and properties"
    ]
  ],
  "openalex": "W7213354508",
  "pdf_url": "https://chemrxiv.org/doi/pdf/10.26434/chemrxiv.15008874/v1",
  "pmcid": null,
  "pmid": null,
  "published": "2026-09-15",
  "publisher": "American Chemical Society (ACS)",
  "ris": "https://research.draconitic.com/paper/8fzzt0pqvagpf.ris",
  "sources": [
    {
      "first_seen": "2026-10-30T12:17:19Z",
      "native_id": "10.26434/chemrxiv.15008874",
      "source": "chemrxiv",
      "url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008874/v1"
    }
  ],
  "subjects": [
    {
      "field": "chemistry",
      "origin": "openalex:2507|Polymer crystallization and properties",
      "subfield": "materials-polymers"
    }
  ],
  "title": "Vicinal Chlorination of Dehydrogenated Polyethylene Toward Applications of Waste Polyolefins",
  "title_text": "Vicinal Chlorination of Dehydrogenated Polyethylene Toward Applications of Waste Polyolefins",
  "type": "preprint",
  "updated_at": "2026-10-30T12:17:19Z",
  "url": "https://research.draconitic.com/paper/8fzzt0pqvagpf",
  "venue": "ChemRxiv",
  "versions": []
}