{
  "abstract": "Post-functionalization and the upcycling of post-consumer waste are valuable strategies for enhancing the material properties and value of polymers, but predictive modeling of these reactions is limited because of their inherent randomness. We present a mathematical framework to describe the effect of polymer functionalization reactions on downstream material properties or products using a combinatoric atomistic probability distribution (APD). The APD is derived generally to predict the spacing of subchains, Δ, between substituents or at chain ends when S substituents are randomly distributed along a polymer chain of length L. This approach is applied to a model upcycling system: the functionalization of polyethylene (PE) via sulfonation and subsequent H 2 O 2 -driven oxidative depolymerization. By coupling the APD with models for downstream depolymerization of sulfonated PE and hydroxyl radical-mediated decomposition kinetics, we develop a kinetic probability distribution (KPD) that explicitly describes the resulting degradation products. This approach results in dimensional reduction by requiring 14 total parameters for an N-species system (N = 6 here), while traditional modeling approaches require 4N + 7 (31 in our case). Probability parameters obtained from the KPD enabled the calculation of product and CO 2 carbon yields within ~10% of experimental values. This framework presents a novel approach to incorporating the underlying randomness governing polymer functionalization reactions, vastly reducing the parameter space and improving targeting of more economically relevant products during upcycling.",
  "abstract_shown": true,
  "affiliations": [
    "Chemical Engineering and Materials Science",
    "Michigan State University",
    "Computer Science",
    "University Illinois"
  ],
  "article_type": null,
  "arxiv": null,
  "author_total": 5,
  "authors": [
    {
      "affs": [
        0,
        1
      ],
      "name": "Brandon D. Howard",
      "orcid": "0000-0002-2587-9889"
    },
    {
      "affs": [
        2,
        3
      ],
      "name": "Christian J. Howard",
      "orcid": "0009-0009-5813-3643"
    },
    {
      "affs": [
        0,
        1
      ],
      "name": "Aspen Tapley",
      "orcid": "0009-0004-6118-4293"
    },
    {
      "affs": [
        0,
        1
      ],
      "name": "John R. Dorgan",
      "orcid": "0000-0001-5277-4508"
    },
    {
      "affs": [
        0,
        1
      ],
      "name": "Scott Calabrese Barton",
      "orcid": "0000-0002-1407-0275"
    }
  ],
  "bibtex": "https://research.draconitic.com/paper/azzvbv6h4f1f4.bib",
  "cited_by": 0,
  "doi": "10.26434/chemrxiv.15009226/v1",
  "fulltext_url": null,
  "id": "azzvbv6h4f1f4",
  "issns": [],
  "landing_url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15009226/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": "W7213979563",
  "pdf_url": null,
  "pmcid": null,
  "pmid": null,
  "published": "2026-09-22",
  "publisher": "American Chemical Society (ACS)",
  "ris": "https://research.draconitic.com/paper/azzvbv6h4f1f4.ris",
  "sources": [
    {
      "first_seen": "2026-10-30T12:17:21Z",
      "native_id": "10.26434/chemrxiv.15009226",
      "source": "chemrxiv",
      "url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15009226/v1"
    }
  ],
  "subjects": [
    {
      "field": "chemistry",
      "origin": "openalex:2507|Polymer crystallization and properties",
      "subfield": "materials-polymers"
    }
  ],
  "title": "Atomistic Probability Kinetic Modeling of Polymer Functionalization: A Framework for Post-Functionalization and Upcycling of Polymers",
  "title_text": "Atomistic Probability Kinetic Modeling of Polymer Functionalization: A Framework for Post-Functionalization and Upcycling of Polymers",
  "type": "preprint",
  "updated_at": "2026-10-30T12:17:21Z",
  "url": "https://research.draconitic.com/paper/azzvbv6h4f1f4",
  "venue": "ChemRxiv",
  "versions": []
}