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Ring-Opening Polymerization of Cyclic Esters and Carbonates with (Thio)urea/Cyclopropenimine Organocatalytic Systems

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Download Hi-Res ImageDownload to MS-PowerPointCite This:ACS Macro Lett. 2024, 13, 2, 181-188
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    Ring-Opening Polymerization of Cyclic Esters and Carbonates with (Thio)urea/Cyclopropenimine Organocatalytic Systems
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    ACS Macro Letters

    Cite this: ACS Macro Lett. 2024, 13, 2, 181–188
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    https://doi.org/10.1021/acsmacrolett.3c00716
    Published January 22, 2024
    Copyright © 2024 American Chemical Society
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    Abstract

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    Organocatalyzed ring-opening polymerization is a powerful tool for the synthesis of a variety of functional, readily degradable polyesters and polycarbonates. We report the use of (thio)ureas in combination with cyclopropenimine bases as a unique catalyst for the polymerization of cyclic esters and carbonates with a large span of reactivities. Methodologies of exceptionally effective and selective cocatalyst combinations were devised to produce polyesters and polycarbonates with narrow dispersities (Đ = 1.01–1.10). Correlations of the pKa of the various ureas and cyclopropenimine bases revealed the critical importance of matching the pKa of the two cocatalysts to achieve the most efficient polymerization conditions. It was found that promoting strong H-bonding interactions with a noncompetitive organic solvent, such as CH2Cl2, enabled greatly increased polymerization rates. The stereoselective polymerization of rac-lactide afforded stereoblock poly(lactides) that crystallize as stereocomplexes, as confirmed by wide-angle X-ray scattering.

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    Supporting Information

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acsmacrolett.3c00716.

    • Experimental supporting data, pKa determination methods, and characterization data (NMR spectra, SEC chromatograms, DSC thermograms, and WAXS data) (PDF)

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    Cited By

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    This article is cited by 2 publications.

    1. Xiaowei Geng, Xiong Liu, Qinglei Yu, Chengjian Zhang, Xinghong Zhang. Advancing H-Bonding Organocatalysis for Ring-Opening Polymerization: Intramolecular Activation of Initiator/Chain End. Journal of the American Chemical Society 2024, 146 (37) , 25852-25859. https://doi.org/10.1021/jacs.4c09394
    2. Jia Zhang, Kai Hin Lui, Rachele Zunino, Yuan Jia, Romain Morodo, Niklas Warlin, James L. Hedrick, Giovanni Talarico, Robert M. Waymouth. Highly Selective O-Phenylene Bisurea Catalysts for ROP: Stabilization of Oxyanion Transition State by a Semiflexible Hydrogen Bond Pocket. Journal of the American Chemical Society 2024, 146 (32) , 22295-22305. https://doi.org/10.1021/jacs.4c04740
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    ACS Macro Letters

    Cite this: ACS Macro Lett. 2024, 13, 2, 181–188
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acsmacrolett.3c00716
    Published January 22, 2024
    Copyright © 2024 American Chemical Society
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