{
  "abstract": "Boron carbide in a hydrogenous polymer is a standard thermal-neutron shield. Under a preliminary cross-section estimate, poly(vinyl chloride) (PVC) reaches the absorption of high-density polyethylene carrying 10 wt% B4C with 6.2 wt%, and so needs less filler and less coupling agent. Whether an aminosilane coupling agent is inert toward such a matrix was examined computationally. Substitution and HCl elimination by the pendant amine at a backbone C–Cl unit were located as verified transition states for free and grafted models, sampled conformationally and compared over a range of dielectric environments. The semiempirical GFN2-xTB and GFN1-xTB methods favor elimination through the zero-point advantage of a synchronous proton transfer. Dispersion-corrected hybrid density functional theory (DFT) does not: its elimination transition state is asynchronous, the zero-point advantage falls from 16 to 7 kJ mol−1, and substitution is favored by 12 to 19 kJ mol−1 (single transition-state conformers, mixed DFT/GFN2-xTB Hessians). The semiempirical prediction of dominant elimination is therefore unreliable; the coupling agent most likely reacts with PVC mainly by N-alkylation, although no product ratio for a real composite follows. At the DFT level, the half-life of a grafted amine at 453 K is on the order of hours to days, an order-of-magnitude estimate for an idealized bimolecular encounter. The minor elimination channel leaves allylic C–Cl bonds 76.5 kJ mol−1 weaker than the backbone. For PVC-matrix shields, non-basic methacryloxypropyl and glycidoxypropyl silanes, which carry no nucleophilic nitrogen, are the safer choice where amine-induced HCl loss and ammonium chloride formation at the interface are to be avoided, as far as the amine-mediated pathways studied here are concerned.",
  "abstract_shown": true,
  "affiliations": [
    "Department of Chemistry and Chemical Processing Technologies, Çaycuma Food and Agriculture Vocational School, Zonguldak Bülent Ecevit University, 67900 Zonguldak, Türkiye"
  ],
  "article_type": null,
  "arxiv": null,
  "author_total": 1,
  "authors": [
    {
      "affs": [
        0
      ],
      "name": "Yetkin Senemoğlu",
      "orcid": "0000-0002-8379-2933"
    }
  ],
  "bibtex": "https://research.draconitic.com/paper/58vfj1mn1c4yq.bib",
  "cited_by": 0,
  "doi": "10.3390/nano16201316",
  "fulltext_url": null,
  "id": "58vfj1mn1c4yq",
  "issns": [
    "2079-4991"
  ],
  "landing_url": "https://www.mdpi.com/2079-4991/16/20/1316",
  "language": null,
  "licence": "CC-BY-4.0",
  "licence_label": "CC BY 4.0",
  "licence_source": "article",
  "licence_url": "https://creativecommons.org/licenses/by/4.0/",
  "metadata_licence": null,
  "native_subjects": [
    [
      "openalex",
      "2507|Polymer Science and PVC"
    ]
  ],
  "openalex": "W7222987658",
  "pdf_url": null,
  "pmcid": null,
  "pmid": null,
  "published": "2026-10-18",
  "publisher": "MDPI AG",
  "ris": "https://research.draconitic.com/paper/58vfj1mn1c4yq.ris",
  "sources": [
    {
      "first_seen": "2026-10-30T12:18:45Z",
      "native_id": "10.3390/nano16201316",
      "source": "crossref",
      "url": "https://www.mdpi.com/2079-4991/16/20/1316"
    }
  ],
  "subjects": [
    {
      "field": "chemistry",
      "origin": "openalex:2507|Polymer Science and PVC",
      "subfield": "materials-polymers"
    }
  ],
  "title": "Aminosilane Coupling Agents at the Boron Carbide/Poly(Vinyl Chloride) Interface: Substitution, Minor Dehydrochlorination and C–Cl Bond Weakening",
  "title_text": "Aminosilane Coupling Agents at the Boron Carbide/Poly(Vinyl Chloride) Interface: Substitution, Minor Dehydrochlorination and C–Cl Bond Weakening",
  "type": "peer-reviewed",
  "updated_at": "2026-10-30T12:18:45Z",
  "url": "https://research.draconitic.com/paper/58vfj1mn1c4yq",
  "venue": "Nanomaterials",
  "versions": []
}