{
  "abstract": "Introducing degradability into conventional vinyl polymers without sacrificing the versatility of radical polymerization remains a major challenge. Radical Ring-Opening Polymerization (rROP) is currently the most promising technique to impart degradability into vinyl-based polymers through the copolymerization of cyclic monomers with common vinyl monomers. However, among the various families of cyclic monomers reported to date, none simultaneously combines high efficiency, versatility, and compatibility with industrial-scale production. Here, we report a family of silylated cyclic allylic sulfides (CAS) designed to decouple radical ring-opening reactivity from post-polymerization cleavage. The representative monomer LC1 combines a CAS scaffold, which undergoes efficient radical addition–fragmentation, with an independently cleavable silyl ether linkage. LC1 is prepared in two steps from readily available precursors, and a simultaneous dual-feed strategy enables its facile and reproducible scale-up. LC1 displays monomer-dependent reactivity across several vinyl monomer families and introduces cleavable junctions throughout chain growth. Kinetic experiments, Mayo analysis and density functional theory reveal two distinct addition–fragmentation processes: rapid ring-opening incorporation of cyclic LC1 followed by a slower secondary transfer pathway involving the pendant allylic functionality generated after ring opening. The resulting polymers undergo backbone fragmentation under fluoride, acidic, basic and Lewis-acid conditions, with degradation kinetics further tunable through pH and silicon substitution. LC1 also remains compatible with emulsion polymerization and crosslinked networks, enabling chemically and thermally triggered disassembly of 3D-printed materials. Finally, in the context of upcycling, hydroxyl-terminated degradation fragments can be repurposed as polyol precursors for polyurethane network formation. This work establishes silylated CAS monomers as a versatile platform for independently programming radical polymer growth and material lifetime.",
  "abstract_shown": true,
  "affiliations": [
    "Aix-Marseille University CNRS, Institut de Chimie Radicalaire, UMR",
    "Université de Haute-Alsace, CNRS, IS2M UMR",
    "CNRS",
    "Institut Galien Paris-Saclay",
    "COATEX SAS",
    "ARKEMA, CERDATO"
  ],
  "article_type": null,
  "arxiv": null,
  "author_total": 15,
  "authors": [
    {
      "affs": [
        0
      ],
      "name": "Luna Choulot"
    },
    {
      "affs": [
        0
      ],
      "name": "Sophia Kouider"
    },
    {
      "affs": [
        0
      ],
      "name": "Maxime Ria"
    },
    {
      "affs": [
        1
      ],
      "name": "Hassiba Boutarfa"
    },
    {
      "affs": [
        1
      ],
      "name": "Loic Buchon"
    },
    {
      "affs": [
        2,
        3
      ],
      "name": "Teodora Tomovic"
    },
    {
      "affs": [
        0
      ],
      "name": "Didier Gigmes"
    },
    {
      "affs": [
        0
      ],
      "name": "Didier Siri"
    },
    {
      "affs": [
        2,
        3
      ],
      "name": "Julien Nicolas"
    },
    {
      "affs": [
        0
      ],
      "name": "Laurence Charles"
    },
    {
      "affs": [
        1
      ],
      "name": "Olivier Soppera"
    },
    {
      "affs": [
        0
      ],
      "name": "Catherine Lefay"
    },
    {
      "affs": [
        4
      ],
      "name": "Guillaume Michaud"
    },
    {
      "affs": [
        5
      ],
      "name": "Jean-Jacques Flat"
    },
    {
      "affs": [
        0
      ],
      "name": "Yohann Guillaneuf",
      "orcid": "0000-0002-5390-1553"
    }
  ],
  "bibtex": "https://research.draconitic.com/paper/eh8axvxsg0hw6.bib",
  "cited_by": 0,
  "doi": "10.26434/chemrxiv.15010975/v1",
  "fulltext_url": null,
  "id": "eh8axvxsg0hw6",
  "issns": [],
  "landing_url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010975/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",
      "1605|Advanced Polymer Synthesis and Characterization"
    ]
  ],
  "openalex": "W7223340739",
  "pdf_url": "https://chemrxiv.org/doi/pdf/10.26434/chemrxiv.15010975/v1",
  "pmcid": null,
  "pmid": null,
  "published": "2026-10-23",
  "publisher": "American Chemical Society (ACS)",
  "ris": "https://research.draconitic.com/paper/eh8axvxsg0hw6.ris",
  "sources": [
    {
      "first_seen": "2026-10-30T12:17:26Z",
      "native_id": "10.26434/chemrxiv.15010975",
      "source": "chemrxiv",
      "url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010975/v3"
    }
  ],
  "subjects": [
    {
      "field": "chemistry",
      "origin": "openalex:1605|Advanced Polymer Synthesis and Characterization",
      "subfield": "organic"
    }
  ],
  "title": "A Readily Scalable Silylated Cyclic Allyl Sulfide Monomer for Degradable Vinyl Polymers",
  "title_text": "A Readily Scalable Silylated Cyclic Allyl Sulfide Monomer for Degradable Vinyl Polymers",
  "type": "preprint",
  "updated_at": "2026-10-30T12:17:26Z",
  "url": "https://research.draconitic.com/paper/eh8axvxsg0hw6",
  "venue": "ChemRxiv",
  "versions": []
}