Study of new chemical derivatization techniques for lignin analysis by size exclusion chromatography Esakkiammal Sudha Esakkimuthu To cite this version: Esakkiammal Sudha Esakkimuthu. Study of new chemical derivatization techniques for lignin analysis by size exclusion chromatography. Material chemistry. Université Grenoble Alpes [2020-..], 2020. English. NNT : 2020GRALI004. tel-02612598 HAL Id: tel-02612598 https://tel.archives-ouvertes.fr/tel-02612598 Submitted on 19 May 2020 HAL is a multi-disciplinary open access L’archive ouverte pluridisciplinaire HAL, est archive for the deposit and dissemination of sci- destinée au dépôt et à la diffusion de documents entific research documents, whether they are pub- scientifiques de niveau recherche, publiés ou non, lished or not. 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THÈSE Pour obtenir le grade de DOCTEUR DE L'UNIVERSITE GRENOBLE ALPES Spécialité : 2MGE : Matériaux, Mécanique, Génie civil, Electrochimie Arrêté ministériel : 25 mai 2016 Présentée par Esakkiammal Sudha ESAKKIMUTHU Thèse dirigée par Gérard MORTHA, Professeur, Grenoble INP et Co-encadrée par Nathalie MARLIN, Maître de Conférences, Grenoble INP préparée au sein du Laboratoire Génie des Procédés Papetiers (LGP2) dans l'École Doctorale I-MEP2 - Ingénierie - Matériaux, Mécanique, Environnement, Energétique, Procédés, Production Étude de nouvelles techniques de derivation chimique de la lignine en vue de l'analyse par chromatographie d'exclusion stérique Thèse soutenue publiquement le 30 janvier 2020, devant le jury composé de : Monsieur Nicolas BROSSE Professeur des Universités, Université de Lorraine, Rapporteur Monsieur Christophe GEANTET Directeur de Recherche, CNRS, Université Lyon 1, Rapporteur Monsieur Sami HALILA Chargé de Recherche, CNRS, Université Grenoble Alpes, Examinateur Monsieur Gérard MORTHA Professeur des Universités, Grenoble INP, Directeur de thèse Madame Nathalie MARLIN Maître de Conférences, Grenoble INP, Co-encadrante Madame Marie-Christine BROCHIER-SALON Ingénieur de Recherche, Grenoble INP, Invitée Monsieur Dominique LACHENAL Professeur des Universités, Émérite, Grenoble INP, Invité 2 I would like to dedicate my thesis to my beloved mother “Mrs. Parvathi” 3 4 Acknowledgements First of all, I am very grateful to my supervisors Prof. Gérard Mortha and Dr. Nathalie Marlin for providing me this opportunity to pursue my research career. I would like to thank Prof. Gerard for his wonderful guidance in analytical chemistry techniques, his guidance encourages and enlarges my research knowledge and become an independent. I would like to express my sincere gratitude to Dr. Nathalie for her constant guidance and motivation throughout my thesis. During my critical situation, my supervisors understood and came forward to bring me out and move on. I am so lucky to have them as my thesis supervisors. Without their support, I would not accomplish this thesis. I like to thank Dr. Marie-Christine Brochier-Salon for part of my thesis work and I learnt a lot about NMR techniques from her. I also thank, for her kindness and support. I would like to thank jury members: Prof. Nicolas Brosse and Dr. Christophe Geantet and Dr. Sami Halila for accepting the invitation. Thanks to Prof. Dominique Lachenal, Dr. Marie-Christine Brochier-Salon for being part of my thesis jury. Thanks to Dr. Luis Serrano, post doc for the collaborative work under the Qualin project, and thanks to Dr. Fanny Bardot for the discussions on the lignin chemistry during my post-master program. I would like to thank Prof. Christine Chirat and Prof. Dominique Lachenal for their support before and during my PhD work. Thanks to all professors in Grenoble INP-Pagora, Prof. Naceur Belgacem, Prof. Alain dufresne and Prof. Julien Bras. Thanks to the Biochip technicians, David and Karine helped me a lot to learn new instruments and to have hands-on experience with all analytical instruments. Thanks to Jessie, a technician, for helping me during final stage of my thesis. My special thanks to French ministry and the doctoral school ED-IMEP2 for funding and providing me the great opportunity to perform my thesis. Thanks to Mme. Augustine Alessio for her great support from the school. I express my thanks to Elsa, who helped me in various aspects, motivated me to apply teaching assistant, conferences etc. and also for her love and friendship. Also, I like to thank my senior colleague Jennifer, Claire and Chamseddine. Thanks to Lakshmanan anna and Seema for introducing about the post-master course and internship. Thanks to my friends Axelle, Amina, Helene, Jahan, Camille, Gabrielle, Hugo, Johanna, Manon, Fleur, Hippolyte and Flavien. They were all in my side during the hard situations to step-out of it. 5 I would also like to thank the administrative unit and Mme. Sylvie and HR department Mme. Anne Marie, M. Stephane Vernac, Mme. Laurence Platel for their help in sorting-out administrative things. Thanks to IT service M. Franck and Mme. Lydia for their good service and friendly nature. Once again thanks to Dr. Nathalie for giving the opportunity to work as a teaching assistant and also to Mme. Sandrine. I like to express my sincere thanks to Sridevi Akka and Raja Anna, for motivating me to continue my career and pursue the PhD, It is ever long memory for me. Thanks to Manikandan Anna and Kabila Akka, you are always with us during our hard time. My particular thanks to my parents Parvathi-Esakkimuthu and my uncle Selvaraj and aunty Ammachi. Without them, I would not establish my career. I wish to thank my family members, my sisters Shenbaga Devi and Indra, brother in-laws, Prabhakaran and Nagarajan, aththai-mama Sakthi-Ramar, father-in-law Ponnuchamy, mother-in-law Muthumariammal and sister-in-law Sangeetha and kutties Harini and Siddarth. My special thanks go to my beloved husband Veerapandian. Without his endless love and support, I would not succeed and thanks to my lovable boy Esakki Parthiban for his cooperation (not crying a lot) to complete my thesis. 6 7 8 Introduction Lignocellulosic biomass is considered as the main renewable source for conversion into wide range of value-added applications and products, which could immensely replace fossil fuel dependency. The biomass macromolecular components are mainly cellulose, hemicelluloses and lignin. Lignin is the second most abundant biopolymer on earth after cellulose and it possesses a highly-branched, three-dimensional aromatic structure with a variety of functional groups and chemical linkages. In particular, lignin is bearing hydroxyl, methoxyl, carbonyl and carboxyl groups. In the last few decades, researchers have made great efforts to characterize lignin for establishing the synthesis formulation of various materials. Lignin is extensively used as a precursor for different applications such as phenolic resins, surfactants, polyurethanes, epoxides, acrylics, and many other products. The characterization of lignin in terms of chemical linkages, structural features, functional groups and polymer chain length is of primary importance to evaluate the possible lignin applications. Numerous analytical methods and techniques have been employed for lignin structural characterization and reactivity study. Amongst, functional groups quantification (phenolic and alcoholic hydroxyls, carbonyls and carboxyls) after lignin derivatization by various analytical techniques, including wet chemical methods, and molar mass distribution (MMD) by size exclusion chromatography (SEC), are the most prominent methods. However, MMD analysis for lignin is more complex than for many other polymers due to the irregular, polar and partially branched structure of lignin, leading to low solubility and partial aggregation in most SEC solvents. As a consequence, SEC provides rather inaccurate results, which limits the possibilities for lignin valorisation and new applications. Most studies focused on the possible chemical modifications of lignin hydroxyl groups to decrease lignin polarity and to improve its dissolution in different solvents. Till date, acetylation is the most widely used derivatization method prior to SEC analysis. However, it exhibits several drawbacks; typically, incomplete solubility, association effect between the molecules and aggregation inside the column, etc. A majority of the lignin MMD studies have applied conventional SEC analysis using polystyrene as standard polymer column calibration, due to the lack of lignin calibrants, and UV and DRI (Differential Refractive Index) as in-line detectors. One important factor that mainly affects the MMD results is the type of calibration standard used; polystyrene in most studies. Indeed, lignin structural conformation is totally different from polystyrene, which leads to unreliable molar mass data. The main objective of this PhD work was thus to improve the SEC performance in the case of lignin, by enhancing its solubility in various solvents using derivatization. Three different 9 derivatization methods were compared: acetylation, fluorobenzylation and fluorobenzoylation. The two latter methods have been developed by Prof. M. Barrelle and collaborators about twenty years ago, but never tested extensively for SEC application. In this study, lignin reactivity during the derivatization reactions has been assessed using various analytical methods (UV, IR, GC, 1H NMR, 13C