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PreprintCC BYChemRxiv

Electronic Control of Composition in Multicomponent oDCPD Fragment Functionalization

  • Janna Jeschke1,2
  • Mariel J. Price2
  • Jeremiah A. Johnson2
  • Hatice Mutlu1,3,4,5,6
6 affiliations
  1. 1Institut de Science des Matériaux de Mulhouse (IS2M), UMR 7361, Université de Haute Alsace (UHA), 15 rue Jean Starcky, 68057 Mulhouse, France
  2. 2Department of Chemistry, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, MA 02139, U.S.A.
  3. 3Technical Polymer Chemistry, Department of Chemistry, Rheinland-Pfälzische Technische Universität Kaiserslautern-Landau (RPTU), Kaiserslautern, 67663, Germany
  4. 4Helmholtz-Zentrum Berlin für Materialien und Energie GmbH, Helmholtz Institute for Polymers in Energy Applications Jena (HIPOLE Jena), Jena, Germany
  5. 5Leibniz-Institut für Verbundwerkstoffe (IVW) GmbH, Kaiserslautern, 67663 Germany
  6. 6Friedrich Schiller University Jena, Institute of Organic Chemistry and Macromolecular Chemistry, Jena, Germany
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Abstract

Deconstruction of poly(dicyclopentadiene)-co-cleavable comonomer (pDCPD-co-CC) thermosets generates oligomers with C=C bonds amenable to chemical functionalization; strategies for doing so remain limited. We report a one-step electrophilic multicomponent post-polymerization modification of deconstruction-relevant model hydroxyl-terminated poly(dicyclopentadiene) oligomers (oDCPD-OH), installing bromine, ether, and sulfonamide motifs. Sulfonamide substituent electronics influence apparent alkene conversion and sulfonamide functional group installation in the isolated oligomers, with electron-poor aryl sulfonamides yielding higher functionalization than electron-rich aryl sulfonamides (32 mol%, and 1 mol%, respectively). Mixed p-CF3/p-NO2 sulfonamide feeds (9:1–1:3) were examined, systematically varying oligomer composition. The incorporated fraction of p-NO2 ranges from 18 to 86%, consistently exceeding its feed fraction and indicating preferential incorporation under competitive conditions. Functionalized fragments show composition-dependent thermal decomposition, with thermal decomposition temperature (Td,5%) ranging from 126 to 176 °C. These results establish electronically guided multicomponent post-polymerization functionalization as a strategy for systematically modulating oDCPD fragment composition.

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Cite

BibTeXRIS
BibTeX
@misc{jeschke2026electronic,
  title = {{Electronic Control of Composition in Multicomponent oDCPD Fragment Functionalization}},
  author = {Janna Jeschke and Mariel J. Price and Jeremiah A. Johnson and Hatice Mutlu},
  howpublished = {ChemRxiv},
  year = {2026},
  month = sep,
  doi = {10.26434/chemrxiv.15009327/v1},
  url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15009327/v1},
  note = {CC BY},
}
RIS
TY  - UNPB
TI  - Electronic Control of Composition in Multicomponent oDCPD Fragment Functionalization
AU  - Janna Jeschke
AU  - Mariel J. Price
AU  - Jeremiah A. Johnson
AU  - Hatice Mutlu
PY  - 2026
DA  - 2026/09/22
PB  - ChemRxiv
DO  - 10.26434/chemrxiv.15009327/v1
UR  - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15009327/v1
AB  - Deconstruction of poly(dicyclopentadiene)-co-cleavable comonomer (pDCPD-co-CC) thermosets generates oligomers with C=C bonds amenable to chemical functionalization; strategies for doing so remain limited. We report a one-step electrophilic multicomponent post-polymerization modification of deconstruction-relevant model hydroxyl-terminated poly(dicyclopentadiene) oligomers (oDCPD-OH), installing bromine, ether, and sulfonamide motifs. Sulfonamide substituent electronics influence apparent alkene conversion and sulfonamide functional group installation in the isolated oligomers, with electron-poor aryl sulfonamides yielding higher functionalization than electron-rich aryl sulfonamides (32 mol%, and 1 mol%, respectively). Mixed p-CF3/p-NO2 sulfonamide feeds (9:1–1:3) were examined, systematically varying oligomer composition. The incorporated fraction of p-NO2 ranges from 18 to 86%, consistently exceeding its feed fraction and indicating preferential incorporation under competitive conditions. Functionalized fragments show composition-dependent thermal decomposition, with thermal decomposition temperature (Td,5%) ranging from 126 to 176 °C. These results establish electronically guided multicomponent post-polymerization functionalization as a strategy for systematically modulating oDCPD fragment composition.
ER  -