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PreprintCC BYChemRxiv

A Highly Proton-Tolerant Multicenter Borane/Phosphazene Catalytic System for Efficient PO/CO2 Copolymerization toward CO2-Based Poly(carbonate-ether) Polyols

  • Minghao Liu1,2
  • Lihang Jiang1,2
  • Zehao Wang3
  • Chenyao Yuan4,2
  • Zhenwei Zhou1,2
  • Jinbo Zhang1,2
  • Shaofeng Liu1,2
  • Zhibo Li1,2,3,4
4 affiliations
  1. 1State Key Laboratory of Advanced Optical Polymer and Manufacturing Technology, College of Polymer Science and Engineering
  2. 2Qingdao University of Science and Technology
  3. 3State Key Laboratory of Chemical Engineering and Low-carbon Technology, College of Chemical and Biological Engineering, Zhejiang University, 866 Yuhangtang Road, Hangzhou, Zhejiang, China, 310058
  4. 4Key Laboratory of Optic-electric Sensing and Analytical Chemistry for Life Science, MOE, College of Chemistry and Molecular Engineering
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Abstract

Low-molecular-weight CO2-based poly(carbonate-ether) polyols from ring-opening copolymerization (ROCOP) of propylene oxide (PO) with CO2 are highly desired as soft blocks to synthesize sustainable polyurethanes. However, such process remains great challenges because of the demanding of highly proton-tolerant catalysts. Herein, we report a binary organocatalysis system based on a nanoscopic multicenter borane Lewis acid (POSS-B8) combined with various organobases for the tunable ROCOP of PO and CO2. The confined POSS-B8 framework not only endows excellent tolerance to proton but enables cooperative activation of PO and CO2, thereby facilitating PO/CO2 ROCOP while effectively suppressing the formation of cyclic propene carbonate (cPC). Remarkably, the binary system can tolerate high loadings of chain-transfer agents (up to 400 equivalents), affording low-molecular-weight polycarbonate polyols (0.6 kDa) with narrow dispersity (Ð = 1.16). By tuning POSS-B8 loading and CO2 pressure, both the carbonate content (19-64 mol%) and glass transition temperature (-58.6 to 4.7 °C) of resulting polymers can be modulated. This metal-free and tunable platform offers a versatile strategy for the preparation of CO2-based poly(carbonate-ether) polyols with controlled structure and strong potential for industrial applications.

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Cite

BibTeXRIS
BibTeX
@misc{liu2026highly,
  title = {{A Highly Proton-Tolerant Multicenter Borane/Phosphazene Catalytic System for Efficient PO/CO2 Copolymerization toward CO2-Based Poly(carbonate-ether) Polyols}},
  author = {Minghao Liu and Lihang Jiang and Zehao Wang and Chenyao Yuan and Zhenwei Zhou and Jinbo Zhang and Shaofeng Liu and Zhibo Li},
  howpublished = {ChemRxiv},
  year = {2026},
  month = oct,
  doi = {10.26434/chemrxiv.15010012/v1},
  url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010012/v1},
  note = {CC BY},
}
RIS
TY  - UNPB
TI  - A Highly Proton-Tolerant Multicenter Borane/Phosphazene Catalytic System for Efficient PO/CO2 Copolymerization toward CO2-Based Poly(carbonate-ether) Polyols
AU  - Minghao Liu
AU  - Lihang Jiang
AU  - Zehao Wang
AU  - Chenyao Yuan
AU  - Zhenwei Zhou
AU  - Jinbo Zhang
AU  - Shaofeng Liu
AU  - Zhibo Li
PY  - 2026
DA  - 2026/10/07
PB  - ChemRxiv
DO  - 10.26434/chemrxiv.15010012/v1
UR  - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010012/v1
AB  - Low-molecular-weight CO2-based poly(carbonate-ether) polyols from ring-opening copolymerization (ROCOP) of propylene oxide (PO) with CO2 are highly desired as soft blocks to synthesize sustainable polyurethanes. However, such process remains great challenges because of the demanding of highly proton-tolerant catalysts. Herein, we report a binary organocatalysis system based on a nanoscopic multicenter borane Lewis acid (POSS-B8) combined with various organobases for the tunable ROCOP of PO and CO2. The confined POSS-B8 framework not only endows excellent tolerance to proton but enables cooperative activation of PO and CO2, thereby facilitating PO/CO2 ROCOP while effectively suppressing the formation of cyclic propene carbonate (cPC). Remarkably, the binary system can tolerate high loadings of chain-transfer agents (up to 400 equivalents), affording low-molecular-weight polycarbonate polyols (0.6 kDa) with narrow dispersity (Ð = 1.16). By tuning POSS-B8 loading and CO2 pressure, both the carbonate content (19-64 mol%) and glass transition temperature (-58.6 to 4.7 °C) of resulting polymers can be modulated. This metal-free and tunable platform offers a versatile strategy for the preparation of CO2-based poly(carbonate-ether) polyols with controlled structure and strong potential for industrial applications.
ER  -