Biobased Copolymers via Cationic Ring-Opening Copolymerization of Levoglucosan Derivatives and ϵ-Caprolactone

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Simultaneous ring-opening copolymerization is a powerful strategy for the synthesis of highly functional copolymers from different types of cyclic monomers. Although copolymers are essential to the plastics industry, environmental concerns associated with current fossil-fuel-based synthetic polymers have led to an increasing interest in the use of renewable feedstock for polymer synthesis. Herein, we report a scalable synthetic platform to afford unique polysaccharides with different pendant functional groups from biomass-derived levoglucosan and ϵ-caprolactone via cationic ring-opening copolymerization (cROCOP). Biocompatible and recyclable bismuth triflate was identified as the optimal catalyst for cROCOP of levoglucosan. Copolymers from tribenzyl levoglucosan and ϵ-caprolactone, as well as from tribenzyl and triallyl levoglucosan, were successfully synthesized. The tribenzyl levoglucosan monomer composition ranged from 16% to 64% in the copolymers with ϵ-caprolactone and 22% to 79% in the copolymers with triallyl levoglucosan. The allylic levoglucosan copolymer can be utilized as a renewably derived scaffold to modify copolymer properties and create other polymer architectures via postpolymerization modification. Monomer reactivity ratios were determined to investigate the copolymer microstructure, indicating that levoglucosan-based copolymers have a gradient architecture. Additionally, we demonstrated that the copolymer glass transition temperature (Tg, ranging from −44.3 to 33.8 °C), thermal stability, and crystallization behavior could be tuned based on the copolymer composition. Overall, this work underscores the utility of levoglucosan as a bioderived feedstock for the development of functional sugar-based copolymers with applications ranging from sustainable materials to biomaterials.

Original languageEnglish (US)
Pages (from-to)935-942
Number of pages8
JournalACS Macro Letters
Issue number7
StatePublished - Jul 18 2023

Bibliographical note

Funding Information:
This work was supported and funded by the NSF Center for Sustainable Polymers at the University of Minnesota; a National Science Foundation supported Center for Chemical Innovation (CHE-1901635). The authors acknowledge Emily Prebihalo for her aid in DOSY NMR. The AX-400 NMR data reported in this publication was supported by the Office of the Vice President of Research, College of Science and Engineering, and the Department of Chemistry at the University of Minnesota. The HD-500 and AV-500 NMR data reported in this publication was supported by the Office of the Director, National Institutes of Health, under Award Number S10OD011952. The content is solely the responsibility of the authors and does not necessarily represent the official views of the National Institutes of Health.

Publisher Copyright:
© 2023 American Chemical Society.

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