Functionalisation of Lignin-Derived Diols for the Synthesis of Thermoplastic Polyurethanes and Polyester Resins

The functionalisation of lignin-derived phenolics (guaiacol, 4-propylguaiacol, eugenol, isoeugenol, phenol, <i>m</i>-cresol, catechol, syringol, syringaldehyde, and vanillin) for the synthesis of thermoplastic polyurethanes (PUs) and polyester (PE) resins is herein described. Diols were...

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Main Authors: Rachele N. Carafa, Justin J. S. Kosalka, Brigida V. Fernandes, Unnati Desai, Daniel A. Foucher, Guerino G. Sacripante
Format: Article
Language:English
Published: MDPI AG 2025-06-01
Series:Molecules
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Online Access:https://www.mdpi.com/1420-3049/30/12/2604
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author Rachele N. Carafa
Justin J. S. Kosalka
Brigida V. Fernandes
Unnati Desai
Daniel A. Foucher
Guerino G. Sacripante
author_facet Rachele N. Carafa
Justin J. S. Kosalka
Brigida V. Fernandes
Unnati Desai
Daniel A. Foucher
Guerino G. Sacripante
author_sort Rachele N. Carafa
collection DOAJ
description The functionalisation of lignin-derived phenolics (guaiacol, 4-propylguaiacol, eugenol, isoeugenol, phenol, <i>m</i>-cresol, catechol, syringol, syringaldehyde, and vanillin) for the synthesis of thermoplastic polyurethanes (PUs) and polyester (PE) resins is herein described. Diols were synthesised from phenolics in a one-step reaction using either glycerol carbonate or ethylene carbonate as a greener, solvent-free synthetic route. Nine of the diols were selected for the synthesis of Pus, and two of the diols were used for the synthesis of PE resins, with their physical and thermal properties characterised. Analysis of the PUs by differential scanning calorimetry (DSC) confirmed their amorphous nature, while thermogravimetric analysis (TGA) suggested improved thermal stability for all PUs with the addition of an alkyl or aldehyde substituent on the benzene ring regardless of the diisocyanate used. However, lower PU thermal stabilities were observed with the use of an aliphatic diisocyanate over an aromatic diisocyanate in the absence of an additional substituent. Analysis of the PEs by DSC also confirmed that the clear resins were all amorphous, and gel permeation chromatography (GPC) revealed significantly higher molecular weights and dispersities when an aliphatic diacid was utilised over an aromatic diacid.
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spelling doaj-art-be6dcbc123274f82a8f25672b76e9a902025-08-20T03:27:39ZengMDPI AGMolecules1420-30492025-06-013012260410.3390/molecules30122604Functionalisation of Lignin-Derived Diols for the Synthesis of Thermoplastic Polyurethanes and Polyester ResinsRachele N. Carafa0Justin J. S. Kosalka1Brigida V. Fernandes2Unnati Desai3Daniel A. Foucher4Guerino G. Sacripante5Department of Chemistry and Biology, Toronto Metropolitan University, 350 Victoria Street, Toronto, ON M5B 2K3, CanadaDepartment of Chemistry and Biology, Toronto Metropolitan University, 350 Victoria Street, Toronto, ON M5B 2K3, CanadaDepartment of Chemistry and Biology, Toronto Metropolitan University, 350 Victoria Street, Toronto, ON M5B 2K3, CanadaDepartment of Chemistry and Biology, Toronto Metropolitan University, 350 Victoria Street, Toronto, ON M5B 2K3, CanadaDepartment of Chemistry and Biology, Toronto Metropolitan University, 350 Victoria Street, Toronto, ON M5B 2K3, CanadaDepartment of Chemistry and Biology, Toronto Metropolitan University, 350 Victoria Street, Toronto, ON M5B 2K3, CanadaThe functionalisation of lignin-derived phenolics (guaiacol, 4-propylguaiacol, eugenol, isoeugenol, phenol, <i>m</i>-cresol, catechol, syringol, syringaldehyde, and vanillin) for the synthesis of thermoplastic polyurethanes (PUs) and polyester (PE) resins is herein described. Diols were synthesised from phenolics in a one-step reaction using either glycerol carbonate or ethylene carbonate as a greener, solvent-free synthetic route. Nine of the diols were selected for the synthesis of Pus, and two of the diols were used for the synthesis of PE resins, with their physical and thermal properties characterised. Analysis of the PUs by differential scanning calorimetry (DSC) confirmed their amorphous nature, while thermogravimetric analysis (TGA) suggested improved thermal stability for all PUs with the addition of an alkyl or aldehyde substituent on the benzene ring regardless of the diisocyanate used. However, lower PU thermal stabilities were observed with the use of an aliphatic diisocyanate over an aromatic diisocyanate in the absence of an additional substituent. Analysis of the PEs by DSC also confirmed that the clear resins were all amorphous, and gel permeation chromatography (GPC) revealed significantly higher molecular weights and dispersities when an aliphatic diacid was utilised over an aromatic diacid.https://www.mdpi.com/1420-3049/30/12/2604ligninbiobasedphenolsglycerol carbonateethylene carbonatepolyurethanes
spellingShingle Rachele N. Carafa
Justin J. S. Kosalka
Brigida V. Fernandes
Unnati Desai
Daniel A. Foucher
Guerino G. Sacripante
Functionalisation of Lignin-Derived Diols for the Synthesis of Thermoplastic Polyurethanes and Polyester Resins
Molecules
lignin
biobased
phenols
glycerol carbonate
ethylene carbonate
polyurethanes
title Functionalisation of Lignin-Derived Diols for the Synthesis of Thermoplastic Polyurethanes and Polyester Resins
title_full Functionalisation of Lignin-Derived Diols for the Synthesis of Thermoplastic Polyurethanes and Polyester Resins
title_fullStr Functionalisation of Lignin-Derived Diols for the Synthesis of Thermoplastic Polyurethanes and Polyester Resins
title_full_unstemmed Functionalisation of Lignin-Derived Diols for the Synthesis of Thermoplastic Polyurethanes and Polyester Resins
title_short Functionalisation of Lignin-Derived Diols for the Synthesis of Thermoplastic Polyurethanes and Polyester Resins
title_sort functionalisation of lignin derived diols for the synthesis of thermoplastic polyurethanes and polyester resins
topic lignin
biobased
phenols
glycerol carbonate
ethylene carbonate
polyurethanes
url https://www.mdpi.com/1420-3049/30/12/2604
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