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PreprintCC BY-NCChemRxiv

Decoupling the Thermal Service Limit from Degradability in 3D Printable Covalent Adaptable Networks via Nanohybridization

  • Natanel Jarach1,2,3,4
  • Yael Shenhar1,2,5,6
  • Hanna Dodiuk3,4
  • Samuel Kenig3,4
  • Shlomo Magdassi1,2
6 affiliations
  1. 1Institute of Chemistry
  2. 2Hebrew University of Jerusalem
  3. 3Department of Polymer Materials Engineering, Pernick Faculty of Engineering
  4. 4Shenkar – Engineering. Design. Art
  5. 5Alpha Program, Future Scientist Center
  6. 6Hebrew University Youth Division
Open at sourceDOICite

Abstract

Covalent adaptable networks (CANs) represent a critical advancement in sustainable polymers, yet their deployment is frequently constrained by a trade-off between high thermal service limit and on-demand degradability. Herein, we report an organic-inorganic hybrid polymer architecture that decouples thermomechanical robustness from chemical responsiveness. By integrating rigid polyhedral oligomeric silsesquioxane (AcryloPOSS) nanoclusters into a dynamic lipoic acid-based CAN-type matrix, the POSS cages function as steric nanoscale shields that restrict polymer chain mobility. This structural confinement yields a high activation energy for disulfide exchange (204.9 ± 22.5 kJ mol-1), thereby suppressing macroscopic creep and maintaining network integrity up to 250°C, matching the performance of non-degradable commercial thermosets. Furthermore, the hybrid network exhibits chemical stability over a wide pH range yet undergoes complete dissolution in highly alkaline solutions within 24 hours, decomposing into the building blocks of the hybrid polymer. Utilizing digital light processing 3D printing, we demonstrate a dual-curing strategy to fabricate geometrically complex, high-resolution polymeric objects that balance exceptional durability with closed-loop end-of-life deconstructability.

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Cite

BibTeXRIS
BibTeX
@misc{jarach2026decoupling,
  title = {{Decoupling the Thermal Service Limit from Degradability in 3D Printable Covalent Adaptable Networks via Nanohybridization}},
  author = {Natanel Jarach and Yael Shenhar and Hanna Dodiuk and Samuel Kenig and Shlomo Magdassi},
  howpublished = {ChemRxiv},
  year = {2026},
  month = sep,
  doi = {10.26434/chemrxiv.15009540/v1},
  url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15009540/v1},
  note = {CC BY-NC},
}
RIS
TY  - UNPB
TI  - Decoupling the Thermal Service Limit from Degradability in 3D Printable Covalent Adaptable Networks via Nanohybridization
AU  - Natanel Jarach
AU  - Yael Shenhar
AU  - Hanna Dodiuk
AU  - Samuel Kenig
AU  - Shlomo Magdassi
PY  - 2026
DA  - 2026/09/28
PB  - ChemRxiv
DO  - 10.26434/chemrxiv.15009540/v1
UR  - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15009540/v1
AB  - Covalent adaptable networks (CANs) represent a critical advancement in sustainable polymers, yet their deployment is frequently constrained by a trade-off between high thermal service limit and on-demand degradability. Herein, we report an organic-inorganic hybrid polymer architecture that decouples thermomechanical robustness from chemical responsiveness. By integrating rigid polyhedral oligomeric silsesquioxane (AcryloPOSS) nanoclusters into a dynamic lipoic acid-based CAN-type matrix, the POSS cages function as steric nanoscale shields that restrict polymer chain mobility. This structural confinement yields a high activation energy for disulfide exchange (204.9 ± 22.5 kJ mol-1), thereby suppressing macroscopic creep and maintaining network integrity up to 250°C, matching the performance of non-degradable commercial thermosets. Furthermore, the hybrid network exhibits chemical stability over a wide pH range yet undergoes complete dissolution in highly alkaline solutions within 24 hours, decomposing into the building blocks of the hybrid polymer. Utilizing digital light processing 3D printing, we demonstrate a dual-curing strategy to fabricate geometrically complex, high-resolution polymeric objects that balance exceptional durability with closed-loop end-of-life deconstructability.
ER  -