CO2/epoxides ring-opening copolymerization towards hydroxy-functionalized polycarbonates
Ring-opening copolymerization (ROCOP) of CO2 and epoxides witnesses continued interest to access sustainable polycarbonates. Introduction of an exocyclic functional group onto the epoxides enables to tune and diversify the properties of the resulting CO2-based polycarbonates. Herein, the CO2/benzyl...
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| Main Authors: | , , , |
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| Format: | Article (Journal) |
| Language: | English |
| Published: |
04 Feb 2026
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| In: |
Polymer chemistry
Year: 2026, Volume: 17, Issue: 10, Pages: 1005-1018 |
| ISSN: | 1759-9962 |
| DOI: | 10.1039/D5PY01191D |
| Online Access: | Verlag, kostenfrei, Volltext: https://doi.org/10.1039/D5PY01191D Verlag, kostenfrei, Volltext: https://pubs.rsc.org/en/content/articlelanding/2026/py/d5py01191d 
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| Author Notes: | Nishant Chaudhary, A. Stephen K. Hashmi, Jean-François Carpentier and Sophie M. Guillaume |
| Summary: | Ring-opening copolymerization (ROCOP) of CO2 and epoxides witnesses continued interest to access sustainable polycarbonates. Introduction of an exocyclic functional group onto the epoxides enables to tune and diversify the properties of the resulting CO2-based polycarbonates. Herein, the CO2/benzyl glycidyl ether (BnGE) or CO2/cyclohexene oxide (CHO) ROCOP has been performed, using a bicomponent catalyst system composed of either a {diamino-bisphenolate}MCl (Al, Fe) or {Salphen}CoCl complex or triethylborane (BEt3) as catalyst, combined with bis(triphenylphosphoranylidene)ammonium chloride (PPNCl) as initiator. While the Al/Fe-based catalyst systems selectively returned the corresponding benzyloxymethylene five-membered cyclic carbonate (5CCOBn) with poor activity in the copolymerization of CO2/BnGE, the {Salphen}CoCl/PPNCl and BEt3/PPNCl systems produced poly(benzyl glycidyl ether carbonate) (PBnGEC) with high chemoselectivity (∼80% and >98%) and regioselectivity (>99% and ∼84%), featuring >99% and ∼85% of carbonate linkages, respectively. Investigation of the {Salphen}CoCl/PPNCl and BEt3/PPNCl catalytic systems in the ROCOP of CO2/BnGE/CHO with different comonomers loadings, enabled to prepare a series of tunable P(BnGEC-co-CHC) terpolymers with similar selectivities. Subsequent hydrogenolysis of these hydrophobic polymers using Pd/C resulted in the deprotection of the side-chain benzyloxy moieties, affording the corresponding hydrophilic P(GC-co-CHC) polymers featuring hydroxyl pendant groups; yet, significant degradation of the polycarbonate main chain was observed for hydroxyl contents >15 mol%. Depolymerization of PBnGEC, PCHC and P(BnGEC-co-CHC) using 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) as catalyst quantitatively returned both corresponding 5CCs. In-depth characterizations by NMR spectroscopy, mass spectrometry, SEC, TGA, and DSC analyses supported well-defined protected and deprotected terpolymers with tunable chemical and thermal properties, providing opportunities for biomedical and/or industrial outcomes. |
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| Item Description: | Zuerst veröffentlicht: 04. Februar 2026 Gesehen am 23.03.2026 Im Titel ist die Zahl 2 tiefgestellt |
| Physical Description: | Online Resource |
| ISSN: | 1759-9962 |
| DOI: | 10.1039/D5PY01191D |