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PreprintCC BYChemRxiv

Vicinal Chlorination of Dehydrogenated Polyethylene Toward Applications of Waste Polyolefins

  • Pedro M. Jimenez Antenucci1,2
  • Tingfeng Chen3,2
  • Hoda Shokrollahzadeh Behbahani3,2
  • Huapei Qiu1,2
  • Lucia Lavelle1,2
  • Emily Sidlow1,2
  • Karen I. Winey3,2,4
  • Marisa C. Kozlowski1,2
4 affiliations
  1. 1Department of Chemistry, Roy and Diana Vagelos Laboratories
  2. 2University of Pennsylvania
  3. 3Department of Chemical and Biomolecular Engineering
  4. 4Department of Materials Science and Engineering
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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.

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Cite

BibTeXRIS
BibTeX
@misc{antenucci2026vicinal,
  title = {{Vicinal Chlorination of Dehydrogenated Polyethylene Toward Applications of Waste Polyolefins}},
  author = {Pedro M. Jimenez Antenucci and Tingfeng Chen and Hoda Shokrollahzadeh Behbahani and Huapei Qiu and Lucia Lavelle and Emily Sidlow and Karen I. Winey and Marisa C. Kozlowski},
  howpublished = {ChemRxiv},
  year = {2026},
  month = sep,
  doi = {10.26434/chemrxiv.15008874/v1},
  url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008874/v1},
  note = {CC BY},
}
RIS
TY  - UNPB
TI  - Vicinal Chlorination of Dehydrogenated Polyethylene Toward Applications of Waste Polyolefins
AU  - Pedro M. Jimenez Antenucci
AU  - Tingfeng Chen
AU  - Hoda Shokrollahzadeh Behbahani
AU  - Huapei Qiu
AU  - Lucia Lavelle
AU  - Emily Sidlow
AU  - Karen I. Winey
AU  - Marisa C. Kozlowski
PY  - 2026
DA  - 2026/09/15
PB  - ChemRxiv
DO  - 10.26434/chemrxiv.15008874/v1
UR  - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008874/v1
AB  - 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.
ER  -