Oral presentation

2.2 Towards recyclable lignin-based materials: recent progress in the development of lignin-based vitrimers

Antoine Duval

Dr

University of Strasbourg / Soprema

Co-author(s):
Wissam Benali, University of Strasbourg
Lisa Sougrati, University of Strasbourg
Luc Avérous, University of Strasbourg

Thanks to their high functionality in aliphatic and phenolic OH groups, lignins have long been studied as precursors for crosslinked polymer materials, i.e. thermosets. A major drawback of this material family is its limited circularity. Indeed, crosslinked polymers cannot melt, precluding mechanical recycling.An attractive strategy to overcome this limitation while maintaining high mechanical performance is to introduce dynamic linkages into the polymer networks. Upon heating, the dynamic bonds can rearrange within the networks, allowing easy thermal reprocessing. These dynamic networks, called Covalent Adaptable Networks (CAN), have seen tremendous developments in the past years, especially those based on associative bond exchanges, known as vitrimers. The application of this concept to biobased and aromatic feedstocks such as lignins shows great promise for the elaboration of circular biobased materials [1,2]. Recently, our group focused on the development of vitrimers from different lignin feedstocks. We reported several strategies to elaborate vitrimers containing dynamic ester [3,4] or vinylogous urethane bonds [5,6] from chemically modified lignins. We also introduced phenol-yne dynamic bonds as a new pathway towards lignin-based vitrimers, with the great advantage that chemical modification of lignin is not required to synthesize the materials [7]. The materials can be successfully reprocessed several times, and different strategies for their chemical recycling have also been studied. This presentation will give an overview of these recent advances towards the closed-loop recycling of lignin-based materials.

References:[1] M.A. Lucherelli, A. Duval, L. Avérous, Biobased vitrimers: Towards sustainable and adaptable performing polymer materials, Progress in Polymer Science 127 (2022) 101515. https://doi.org/10.1016/j.progpolymsci.2022.101515.[2] L. Sougrati, A. Duval, L. Avérous, Biobased and aromatic Covalent Adaptable Networks: When architectures meet properties, within the framework of a circular bioeconomy, Materials Science and Engineering: R: Reports 161 (2024) 100882. https://doi.org/10.1016/j.mser.2024.100882.[3] A. Duval, W. Benali, L. Avérous, Turning lignin into a recyclable bioresource: transesterification vitrimers from lignins modified with ethylene carbonate, Green Chem. 26 (2024) 8414–8427. https://doi.org/10.1039/D4GC00567H.[4] A. Duval, W. Benali, L. Avérous, Exploiting Lignin Structure and Reactivity to Design Vitrimers with Controlled Ratio of Dynamic to Non-Dynamic Bonds, ChemSusChem 18 (2025) e202401480. https://doi.org/10.1002/cssc.202401480.[5] L. Sougrati, A. Duval, L. Avérous, From Lignins to Renewable Aromatic Vitrimers based on Vinylogous Urethane, ChemSusChem 16 (2023) e202300792. https://doi.org/10.1002/cssc.202300792.[6] L. Sougrati, A. Duval, L. Avérous, Closed-Loop Recycling of Sustainable Lignin-Based Vinylogous Urethane Vitrimers, (2025). https://doi.org/10.2139/ssrn.5107362.[7] L. Sougrati, A. Duval, L. Avérous, Introducing phenol-yne chemistry for the design of lignin-based vitrimers: towards sustainable and recyclable materials, J. Mater. Chem. A 13 (2025) 4921–4939. https://doi.org/10.1039/D4TA07880B.

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