Lignin-derivable, thermoplastic, non-isocyanate polyurethanes with increased hydrogen-bonding content and toughness vs. petroleum-derived analogues
| Author(s) | Mahajan, Jignesh S. | |
| Author(s) | Hinton, Zachary R. | |
| Author(s) | Nombera Bueno, Eduardo | |
| Author(s) | Epps, Thomas H. III | |
| Author(s) | Korley, LaShanda T. J. | |
| Date Accessioned | 2024-05-30T16:59:28Z | |
| Date Available | 2024-05-30T16:59:28Z | |
| Publication Date | 2024-04-02 | |
| Description | This article was originally published in Materials Advances. The version of record is available at: https://doi.org/10.1039/D4MA00039K. © 2024 The Author(s). Published by the Royal Society of Chemistry | |
| Abstract | The functionality inherent in lignin-derivable bisguaiacols/bissyringols can improve the processability and performance of the resulting polymers. Herein, non-isocyanate polyurethanes (NIPUs) were synthesized from bisguaiacols/bissyringols with varying degrees of methoxy substitution and differing bridging groups. Notably, the presence of increasing numbers of methoxy groups (0, 2, and 4) in bisphenol F (BPF)-, bisguaiacol F (BGF)-, and bissyringol F (BSF)-NIPUs led to higher percentages of hydrogen-bonded –OH/–NH groups (i.e., ∼65%, ∼85%, ∼95%, respectively). Increased hydrogen bonding between chains improved the elongation-at-break (εbreak) and toughness of lignin-derivable NIPUs over their petroleum counterparts without a reduction in Young's moduli and tensile strengths. For example, BSF-NIPU exhibited the highest εbreak ∼210% and toughness ∼62 MJ m−3, followed by BGF-NIPU (εbreak ∼185% and toughness ∼58 MJ m−3), and then BPF-NIPU (εbreak ∼140% and toughness ∼42 MJ m−3). Similar trends were found in the dimethyl-substituted analogues, particularly for the bisphenol A-NIPU and bisguaiacol A-NIPU. Importantly, the melt rheology of the lignin-derivable NIPUs was comparable to that of the petroleum-derived analogues, with a slightly lower viscosity (i.e., improved melt flow) for the bio-derivable NIPUs. These findings suggested that the added functionalities (methoxy groups) derived from lignin precursors improved thermomechanical stability while also offering increased processability. Altogether, the structure–property-processing relationships described in this work can help facilitate the development of sustainable, performance-advantaged polymers. | |
| Sponsor | The authors are grateful for financial support from the Army Research Office under Cooperative Agreement Number W911NF-22-2-0257 (thermal characterization and thermomechanical testing). The authors thank the National Science Foundation under award NSF DMR POL 2004682 (synthesis) and the Center for Plastics Innovation, an Energy Frontier Research Center funded by the US Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences (BES) under award DE-SC0021166 (rheology) for partially supporting this work. The authors acknowledge the University of Delaware (UD) Advanced Materials Characterization Laboratory for the use of the ATR-FTIR, DSC, and TGA instruments and the UD Mass Spectrometry facility for the use of the mass spectrometer. The authors also thank the UD NMR laboratory for the use of the NMR spectrometer, which was partially supported by the Delaware COBRE program, with a grant from the National Institute of General Medical Sciences – NIGMS (5 P30 GM110758-02) from the National Institutes of Health (NIH). The views and findings of the authors expressed herein do not necessarily reflect those of the Army Research Office, NSF, DOE, or NIH. | |
| Citation | Mahajan, Jignesh S., Zachary R. Hinton, Eduardo Nombera Bueno, Thomas H. Epps, Iii, and LaShanda T. J. Korley. “Lignin-Derivable, Thermoplastic, Non-Isocyanate Polyurethanes with Increased Hydrogen-Bonding Content and Toughness vs. Petroleum-Derived Analogues.” Materials Advances 5, no. 9 (2024): 3950–64. https://doi.org/10.1039/D4MA00039K. | |
| ISSN | 2633-5409 | |
| URL | https://udspace.udel.edu/handle/19716/34432 | |
| Language | en_US | |
| Publisher | Materials Advances | |
| dc.rights | Attribution-NonCommercial 4.0 International | en |
| dc.rights.uri | http://creativecommons.org/licenses/by-nc/4.0/ | |
| Title | Lignin-derivable, thermoplastic, non-isocyanate polyurethanes with increased hydrogen-bonding content and toughness vs. petroleum-derived analogues | |
| Type | Article |
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