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Isolation of Low Dispersity Fractions of Acetone Organosolv Lignins to Understand their Reactivity: Towards Aromatic Building Blocks for Polymers Synthesis

Two organosolv lignins extracted during pilot runs of the Fabiola process were analyzed, fractionated and chemically modified with ethylene carbonate (EC) to produce building blocks suitable for polymer synthesis. Isolation of low dispersity fractions relied on the partial solubility of the lignins...

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Autores principales: Duval, Antoine, Layrac, Géraldine, van Zomeren, André, Smit, Arjan T., Pollet, Eric, Avérous, Luc
Formato: Online Artículo Texto
Lenguaje:English
Publicado: John Wiley and Sons Inc. 2020
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7821138/
https://www.ncbi.nlm.nih.gov/pubmed/33006437
http://dx.doi.org/10.1002/cssc.202001976
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author Duval, Antoine
Layrac, Géraldine
van Zomeren, André
Smit, Arjan T.
Pollet, Eric
Avérous, Luc
author_facet Duval, Antoine
Layrac, Géraldine
van Zomeren, André
Smit, Arjan T.
Pollet, Eric
Avérous, Luc
author_sort Duval, Antoine
collection PubMed
description Two organosolv lignins extracted during pilot runs of the Fabiola process were analyzed, fractionated and chemically modified with ethylene carbonate (EC) to produce building blocks suitable for polymer synthesis. Isolation of low dispersity fractions relied on the partial solubility of the lignins in organic solvents. Lignins solubility was first evaluated and analyzed with Hansen and Kamlet‐Taft solubility parameters, showing a good correlation with the solvents dipolarity/polarizability parameter π*. The results were then used to select a sequence of solvents able to fractionate the lignins into low dispersity fractions of increasing molar masses, which were analyzed by (31)P NMR, SEC and DSC. The lignins were then reacted with EC, to convert the phenolic OH groups into primary aliphatic OH groups. The reactivity of the organosolv lignins was high, and milder reaction conditions than previously reported were sufficient to fully convert the phenolic OH groups. A gradual reduction in reactivity with increasing molar mass was evidenced and attributed to reduced solubility of high molar mass fragments in EC. Undesirable crosslinking side reactions were evidenced by SEC, but were efficiently limited thanks to a fine control of the reaction conditions, helping to maximize the benefits of the developed lignin modification with EC.
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spelling pubmed-78211382021-01-26 Isolation of Low Dispersity Fractions of Acetone Organosolv Lignins to Understand their Reactivity: Towards Aromatic Building Blocks for Polymers Synthesis Duval, Antoine Layrac, Géraldine van Zomeren, André Smit, Arjan T. Pollet, Eric Avérous, Luc ChemSusChem Full Papers Two organosolv lignins extracted during pilot runs of the Fabiola process were analyzed, fractionated and chemically modified with ethylene carbonate (EC) to produce building blocks suitable for polymer synthesis. Isolation of low dispersity fractions relied on the partial solubility of the lignins in organic solvents. Lignins solubility was first evaluated and analyzed with Hansen and Kamlet‐Taft solubility parameters, showing a good correlation with the solvents dipolarity/polarizability parameter π*. The results were then used to select a sequence of solvents able to fractionate the lignins into low dispersity fractions of increasing molar masses, which were analyzed by (31)P NMR, SEC and DSC. The lignins were then reacted with EC, to convert the phenolic OH groups into primary aliphatic OH groups. The reactivity of the organosolv lignins was high, and milder reaction conditions than previously reported were sufficient to fully convert the phenolic OH groups. A gradual reduction in reactivity with increasing molar mass was evidenced and attributed to reduced solubility of high molar mass fragments in EC. Undesirable crosslinking side reactions were evidenced by SEC, but were efficiently limited thanks to a fine control of the reaction conditions, helping to maximize the benefits of the developed lignin modification with EC. John Wiley and Sons Inc. 2020-10-16 2021-01-07 /pmc/articles/PMC7821138/ /pubmed/33006437 http://dx.doi.org/10.1002/cssc.202001976 Text en © 2020 The Authors. ChemSusChem published by Wiley-VCH GmbH This is an open access article under the terms of the http://creativecommons.org/licenses/by/4.0/ License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.
spellingShingle Full Papers
Duval, Antoine
Layrac, Géraldine
van Zomeren, André
Smit, Arjan T.
Pollet, Eric
Avérous, Luc
Isolation of Low Dispersity Fractions of Acetone Organosolv Lignins to Understand their Reactivity: Towards Aromatic Building Blocks for Polymers Synthesis
title Isolation of Low Dispersity Fractions of Acetone Organosolv Lignins to Understand their Reactivity: Towards Aromatic Building Blocks for Polymers Synthesis
title_full Isolation of Low Dispersity Fractions of Acetone Organosolv Lignins to Understand their Reactivity: Towards Aromatic Building Blocks for Polymers Synthesis
title_fullStr Isolation of Low Dispersity Fractions of Acetone Organosolv Lignins to Understand their Reactivity: Towards Aromatic Building Blocks for Polymers Synthesis
title_full_unstemmed Isolation of Low Dispersity Fractions of Acetone Organosolv Lignins to Understand their Reactivity: Towards Aromatic Building Blocks for Polymers Synthesis
title_short Isolation of Low Dispersity Fractions of Acetone Organosolv Lignins to Understand their Reactivity: Towards Aromatic Building Blocks for Polymers Synthesis
title_sort isolation of low dispersity fractions of acetone organosolv lignins to understand their reactivity: towards aromatic building blocks for polymers synthesis
topic Full Papers
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7821138/
https://www.ncbi.nlm.nih.gov/pubmed/33006437
http://dx.doi.org/10.1002/cssc.202001976
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