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Modification Et Stabilisation De La Réactivité De Modification et stabilisation de la réactivité de tanins traités chimiquement : applications à la préparation de résines adhésives et de mousses écosoutenables Samuele Giovando To cite this version: Samuele Giovando. Modification et stabilisation de la réactivité de tanins traités chimiquement : applications à la préparation de résines adhésives et de mousses écosoutenables. Alimentation et Nutrition. Université de Lorraine, 2013. Français. NNT : 2013LORR0227. tel-01750522 HAL Id: tel-01750522 https://hal.univ-lorraine.fr/tel-01750522 Submitted on 29 Mar 2018 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. The documents may come from émanant des établissements d’enseignement et de teaching and research institutions in France or recherche français ou étrangers, des laboratoires abroad, or from public or private research centers. publics ou privés. AVERTISSEMENT Ce document est le fruit d'un long travail approuvé par le jury de soutenance et mis à disposition de l'ensemble de la communauté universitaire élargie. Il est soumis à la propriété intellectuelle de l'auteur. Ceci implique une obligation de citation et de référencement lors de l’utilisation de ce document. D'autre part, toute contrefaçon, plagiat, reproduction illicite encourt une poursuite pénale. Contact : [email protected] LIENS Code de la Propriété Intellectuelle. articles L 122. 4 Code de la Propriété Intellectuelle. articles L 335.2- L 335.10 http://www.cfcopies.com/V2/leg/leg_droi.php http://www.culture.gouv.fr/culture/infos-pratiques/droits/protection.htm UFR. ENSTIB Université de Lorraine Ecole Doctorale Sciences et Ingénierie des Ressources Procédés Produits et Environnement Département de Formation Doctorale Sciences du Bois THESE Pour l’obtention du titre de Docteur de l’Université de Lorraine Spécialité : Sciences du Bois Présentée par Samuele GIOVANDO Modification et stabilisation de la réactivité de tanins traités chimiquement : applications à la préparation de résines adhésives et de mousses écosoutenables Soutenance prévue le 14 novembre 2013 devant le jury : Rapporteurs M. Bertrand CHARRIER (Pr, IPREM, UPPA, Pau) M. Frédéric PICHELIN (Pr, HSB-BFH, Biel) Examinateurs M. Luc AVEROUS (Pr, ECPM-ICPEES, Strasbourg) M. André MERLIN (Pr, LERMAB, UL, Nancy) M. Antonio PIZZI (Pr, LERMAB, UL, Nancy) Mme. Béatrice GEORGE (MC, LERMAB, UL, Nancy) ii Remerciements A Les Institutions : • A André Merlin, mon Directeur de thèse, pour la gentillesse de m'accueillir dans son groupe. • A Prof. Antonio Pizzi, mon vrais Directeur de thèse, pour m’avoir chargé à faire sous forme de thèse nos projet de travail. Wow! c’a été possible! • Une autre fois à Tony, pour sa familiarité et sa confiance. Pour la sensation qu’il me donne, d’être en train d’avoir un métier très promissent dans les mains. Peut-être qu’il soit vrais… • A Silvateam et à Antonio, Michele et Stefano Battaglia pour leur confiance en moi et dans ce projet. • A Beatrice George pour sa grande patience et sa disponibilité A La Famille: • A Marilena, mia moglie, che mi spinge a fare, e che ne accetta le conseguenze. • A Beatrice, mia figlia, che ascoltando i miei sproloqui sui polifenoli, li ha ribattezzati i “pony e fagioli”! • A Francesco, mio figlio appena nato, concepito sul percorso della tesi. A Moi: • Au nager à la piscine à penser aux résines de tanins! iii iv Liste des publications et des brevets 1) S.GIOVANDO, A.PIZZI, H.PASCH, K.RODE, Synthetic tanins structure by MALDI- TOF mass spectrometry, J.Appl.Polymer Sci., 114: 1339 - 1347 (2009) 2) A.PIZZI, H.PASCH, K.RODE, S.GIOVANDO, Polymer structure of commercial hydrolysable tanins by MALDI-TOF mass spectrometry, J.Appl.Polymer Sci., 113 (6): 3847-3859 (2009) 3) C.BASSO, V.FIERRO, S.GIOVANDO, A.PIZZI, A.CELZARD, “Composizione per la fabbricazione di un materiale espanso a base di tanini, materiale espanso da essa ottenibile, e relativo procedimento di fabbricazione”, Patent application number (Italy): TO2011A000656 (demande de brevet déposé le 21-07-2011), extended international PCT the 18/07/2012 with n. PCT/EP2012/003031. 4) M.C.BASSO, X.LI, S.GIOVANDO, V.FIERRO, A.PIZZI, A.CELZARD, Green, formaldehyde-free, foams for thermal insulation, Advanced Materials Letters, 2 (6): 378- 382 (2011) 5) S.SPINA, X.ZHOU, C.SEGOVIA, A.PIZZI, M.ROMAGNOLI, S.GIOVANDO, H.PASCH, K.RODE, L.DELMOTTE, Phenolic resin adhesives based on chestnut hydrolysable tanins, J.Adh.Sci.Technol, DOI:10.1080/01694243.2012.697673 (2012) 6) S.GIOVANDO, M.C.BASSO, A.PIZZI, A.CELZARD, “Composizione a base di tanini, priva di formaldeide e di solventi organici bassobollenti, per la produzione di un materiale espanso, e relativo procedimento”, Patent application number (Italy): TO2012A000860 (demande de brevet déposé le 02-10-2012) 7) N.RADEBE, K.RODE, A.PIZZI, S.GIOVANDO, H.PASCH, MALDI-TOF-CID for the Microstructure Elucidation of Polymeric Hydrolysable Tanins, J.Appl.Polym.Sci. 128: 97– 107 (2013), DOI: 10.1002/APP.38156 8) S.GIOVANDO, A.PIZZI, H.PASCH, N.PRETORIUS, Structure and oligomers distribution of commercial Tara (Caesalpina spinosa) hydrolysable tanin , ProLigno, 9 (1): 22-31 (2013) v 9) S.SPINA, X.ZHOU, C.SEGOVIA, A.PIZZI, M.ROMAGNOLI, S.GIOVANDO, H.PASCH, K.RODE, L.DELMOTTE, Phenolic resin adhesives based on chestnut hydrolysable tanins, Intern.Wood Prod.J., 4 (2): 95-100 (2013), DOI: 10.1179/2042645312Y.0000000020 10) M.C.BASSO, S.GIOVANDO, A.PIZZI, A.CELZARD, Tanin/furanic foams without blowing agents and formaldehyde, Ind.Crops&Prods, 49 (2013) 17– 22 vi Résumé L’objectif de ce travail de thèse a été de produire des matériaux expansés à partir de produits d’origine naturelle, en particulier à partir de tanins. Au moment où cette thèse a débuté, des études étaient publiées sur la possibilité d’élaborer ce type de matériaux avec des formulations similaires à celles des colles utilisées pour le bois mais qui comportaient du formaldéhyde. Cela allait à l’encontre du caractère naturel recherché puisqu’en fait, on utilisait des produits naturels et les mélangeait ou les faisait réagir avec des produits synthétiques irritants, toxiques voire cancérogènes. Il n’était donc pas possible de les présenter comme des matériaux « verts ». Aussi, nous avons voulu au cours de ce travail, élaborer des matériaux expansés uniquement à partir de produits naturels ou en découlant. Les tanins sont des substances naturelles chimiquement actives qui peuvent être utilisées afin de remplacer des produits homologues dérivés du pétrole comme le phénol par exemple qui présente des caractéristiques de réactivité chimique très similaires à celles des tanins condensés. Des formulations comportant des tanins condensés ont d’ailleurs déjà été étudiées pour élaborer des matériaux expansés. En considérant cela, ce travail de thèse s’est déroulé sous la forme de différents projets convergents vers un objectif commun : la production de mousses aux tanins plus naturelles et plus intéressantes pour l’industrie. Cinq projets ont ainsi été menés : 1. analyses de différents tanins, condensés, hydrolysables et synthétiques; 2. production de mousses aux tanins sans utilisation de formaldéhyde; 3. production de mousses aux tanins sans solvants; 4. production de mousses aux tanins rigides ou élastiques; 5. production de mousses aux tanins, sans acides, mais avec une catalyse alcaline. vii viii Sommaire Introduction .................................................................... 1 Les tanins ..................................................................... 2 Les tanins synthétiques ................................................... 2 Les tanins végétaux : condensés et hydrolysables .............. 4 Rôle naturel et propriétés .............................................. 5 Processus d’extraction .................................................. 6 Classification générale des tanins: ................................. 22 Réactivité des tanins condensés : .................................... 29 Réaction avec les aldéhydes .......................................... 30 Réactivité avec le glyoxal ............................................. 40 Autocondensation acide ................................................ 41 Autocondensation alcaline ............................................ 43 Autocondensation alcaline catalysée par la silice. ............. 46 L’Alcool Furfurylique ...................................................... 48 Caractéristiques Physico-chimiques ................................ 48 Production de l’Alcool Furfurylique ................................. 49 Réactivité de l’alcool Furfurylique. .................................. 51 Réactivité de l’alcool furfurylique avec les tanins .............. 52 Les Mousses ................................................................. 54 Les mousses solides .................................................... 56 Les mousses naturelles ................................................ 58 Résultats et discussions ................................................... 59 Caractérisation des tanins. ............................................. 61 Structure moléculaire des tanins synthétiques par la spectrométrie de masse MALDI-TOF. .............................. 61 Structure moléculaire des tanins hydrolysables commerciaux par la spectrométrie de masse MALDI-TOF. ..................... 71 MALDI-TOF-CID
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