R´eseaux ´epoxy-amine h´et´erog`enes `a partir de dispersions de microparticules polym`eres r´eticul´ees Marie-Laure Michon To cite this version: Marie-Laure Michon. R´eseaux ´epoxy-amine h´et´erog`enes a` partir de dispersions de micropartic- ules polym`eres r´eticul´ees. Materials. INSA de Lyon, 2014. English. <NNT : 2014ISAL0018>. <tel-01135308> HAL Id: tel-01135308 https://tel.archives-ouvertes.fr/tel-01135308 Submitted on 25 Mar 2015 HAL is a multi-disciplinary open access L’archive ouverte pluridisciplinaire HAL, est archive for the deposit and dissemination of sci- destin´ee au d´epˆot et `a la diffusion de documents entific research documents, whether they are pub- scientifiques de niveau recherche, publi´es ou non, lished or not. The documents may come from ´emanant des ´etablissements d’enseignement et de teaching and research institutions in France or recherche fran¸cais ou ´etrangers, des laboratoires abroad, or from public or private research centers. publics ou priv´es. N° d’ordre: 2014ISAL0018 Année 2014 Thèse Heterogeneous epoxy-amine networks from the dispersion of cross-linked polymer microparticles Présentée devant L’institut national des sciences appliquées de Lyon Pour obtenir Le grade de docteur École doctorale : Matériaux de Lyon Spécialité : Matériaux Polymères et Composites Par Michon Marie-Laure Ingénieur CPE Lyon Soutenue le 14 février 2014 devant la Commission d’examen Jury M. Duskova-Smrckova Researcher, IMC, Prague, République Tchèque M. Dumon Professeur, LCPO, ENSCBP Bordeaux T. McKenna Directeur de recherche CNRS, C2P2, CPE Lyon J. Galy Directrice de recherche CNRS, IMP@INSA, INSA de Lyon J-F. Gérard Professeur, IMP@INSA, INSA de Lyon T. Dikic Dow Chemical, Terneuzen, Pays-Bas T. Verbrugge Dow Chemical, Terneuzen, Pays-Bas Cette thèse est accessible à l'adresse : http://theses.insa-lyon.fr/publication/2014ISAL0018/these.pdf © [M.L. Michon], [2014], INSA de Lyon, tous droits réservés Cette thèse est accessible à l'adresse : http://theses.insa-lyon.fr/publication/2014ISAL0018/these.pdf © [M.L. Michon], [2014], INSA de Lyon, tous droits réservés INSA Direction de la Recherche - Ecoles Doctorales – Quinquennal 2011-2015 SIGLE ECOLE DOCTORALE NOM ET COORDONNEES DU RESPONSABLE CHIMIE DE LYON M. Jean Marc LANCELIN CHIMIE http://www.edchimie-lyon.fr Université de Lyon – Collège Doctoral Bât ESCPE Sec :Renée EL MELHEM 43 bd du 11 novembre 1918 Bat Blaise Pascal 69622 VILLEURBANNE Cedex 3e etage Tél : 04.72.43 13 95 [email protected] Insa : R. GOURDON ELECTRONIQUE, M. Gérard SCORLETTI E.E.A. ELECTROTECHNIQUE, AUTOMATIQUE Ecole Centrale de Lyon http://edeea.ec-lyon.fr 36 avenue Guy de Collongue 69134 ECULLY Secrétariat : M.C. HAVGOUDOUKIAN Tél : 04.72.18 60.97 Fax : 04 78 43 37 17 [email protected] [email protected] EVOLUTION, ECOSYSTEME, Mme Gudrun BORNETTE E2M2 MICROBIOLOGIE, MODELISATION CNRS UMR 5023 LEHNA http://e2m2.universite-lyon.fr Université Claude Bernard Lyon 1 Bât Forel Insa : H. CHARLES 43 bd du 11 novembre 1918 69622 VILLEURBANNE Cédex Tél : 06.07.53.89.13 e2m2@ univ-lyon1.fr INTERDISCIPLINAIRE SCIENCES- Mme Emmanuelle CANET-SOULAS EDISS SANTE INSERM U1060, CarMeN lab, Univ. Lyon 1 http://www.ediss-lyon.fr Bâtiment IMBL 11 avenue Jean Capelle INSA de Lyon Sec : 696621 Villeurbanne Insa : M. LAGARDE Tél : 04.72.68.49.09 Fax :04 72 68 49 16 [email protected] INFORMATIQUE ET Mme Sylvie CALABRETTO INFOMATHS MATHEMATIQUES LIRIS – INSA de Lyon http://infomaths.univ-lyon1.fr Bat Blaise Pascal 7 avenue Jean Capelle Sec :Renée EL MELHEM 69622 VILLEURBANNE Cedex Bat Blaise Pascal Tél : 04.72. 43. 80. 46 Fax 04 72 43 16 87 3e etage [email protected] [email protected] MATERIAUX DE LYON M. Jean-Yves BUFFIERE Matériaux http://ed34.universite-lyon.fr INSA de Lyon MATEIS Secrétariat : M. LABOUNE Bâtiment Saint Exupéry PM : 71.70 –Fax : 87.12 7 avenue Jean Capelle Bat. Saint Exupéry 69621 VILLEURBANNE Cedex [email protected] Tél : 04.72.43 83 18 Fax 04 72 43 85 28 [email protected] MECANIQUE, ENERGETIQUE, GENIE M. Philippe BOISSE MEGA CIVIL, ACOUSTIQUE INSA de Lyon http://mega.universite-lyon.fr Laboratoire LAMCOS Bâtiment Jacquard Secrétariat : M. LABOUNE 25 bis avenue Jean Capelle PM : 71.70 –Fax : 87.12 69621 VILLEURBANNE Cedex Bat. Saint Exupéry Tél :04.72 .43.71.70 Fax : 04 72 43 72 37 [email protected] [email protected] ScSo* M. OBADIA Lionel ScSo http://recherche.univ-lyon2.fr/scso/ Université Lyon 2 86 rue Pasteur Sec : Viviane POLSINELLI 69365 LYON Cedex 07 Brigitte DUBOIS Tél : 04.78.77.23.86 Fax : 04.37.28.04.48 Insa : J.Y. TOUSSAINT [email protected] *ScSo : Histoire, Géographie, Aménagement, Urbanisme, Archéologie, Science politique, Sociologie, Anthropologie Cette thèse est accessible à l'adresse : http://theses.insa-lyon.fr/publication/2014ISAL0018/these.pdf © [M.L. Michon], [2014], INSA de Lyon, tous droits réservés Cette thèse est accessible à l'adresse : http://theses.insa-lyon.fr/publication/2014ISAL0018/these.pdf © [M.L. Michon], [2014], INSA de Lyon, tous droits réservés ACKNOWLEGMENT I would like to express my sincere gratitude to my supervisors Dr. Jocelyne Galy and Prof. Jean- François Gérard. It was a pleasure working with you in the lab every day, sharing results (the successful ones as well as the unexpected ones), and discussing the thesis at great lengths. Thank you for your advice, your continued support and your trust over these past three years. I would also like to thank all the members of the Jury - Dr. Miroslava Duskova-Smrckova, Prof. Michel Dumon and Dr. Timothy McKenna - to have accepted to report on my research study, but also for your encouragements and insightful comments. Thank you to Dr. Tamara Dikic and Tom Verbrugge from the Dow Chemical Company, for taking a chance on me with this research topic, supporting me from the start and collaborating with me during three years. I do not forget their colleagues: Brian Dickie and Sylvie Vervoort for their help with the DSC and rheology experiments. For their help and insightful discussions (scientific or not), thank you to all the members of the IMP lab: Mallou and Isabelle, Raphael, Gilbert and Guilhem, the lunch team at the CNRS restaurant, the people sharing lunch in the “salle à café” and my “co-bureaux” of my two different offices (Vincent, Jean-Marc, Ismail, Nicolas D, Ali, Marco, Loic, Cédric, Julien, Marion T, Damien, Arthur). Thank you for your help, the laughs and more difficult moments we’ve shared! Without forgetting the others students / engineers I have met during these 3 years, “ma jumelle” Marianne, Suzanne and Hélène, Elie, Ludovic, Sylvain, Yann, Nicolas L., Nora, Noellie, Camille, Florianne, Marie C., Maxime, Séphane, Alexia, Marie V, Johanna, Gino, Thibault, Florent, Gabriela, Miren, Marion C., Aymeric F. & G…some of you already know we became friends and that the story will not stop today! Of course thanks to all my friends from Lyon, Avignon and further away (Marie, Micha, Laura, Marion, Else, Milena, Céline, Marie-Claire, Fanny, Anne-Catherine, Lea, Aurélia, Julie, Odile, the wcs team, and to my family. Now for you “ me voilà le seul Docteur de la famille qui ne pourra même pas nous soigner!!” Thanks to my sister Pauline who is “repairing me” so often, and of course also to M- No, JC, Jeanette, Georges, Denise, Agnes, Jean-Jacques, Myriam, Gérard, Maud, Hugo, Nicolas, Auguste, Guilhem, Cyril, Sabrina, Chloe, Anne-Sophie…You were always there when I needed… Merci, Gramaci Cette thèse est accessible à l'adresse : http://theses.insa-lyon.fr/publication/2014ISAL0018/these.pdf © [M.L. Michon], [2014], INSA de Lyon, tous droits réservés Marie-Laure Michon, IMP@INSA, 2014 Cette thèse est accessible à l'adresse : http://theses.insa-lyon.fr/publication/2014ISAL0018/these.pdf © [M.L. Michon], [2014], INSA de Lyon, to us droits réservés Page 6 CONTENTS General introduction ......................................................................................................................... 11 I Literature review ........................................................................................................................ 15 1 Background on epoxy networks .................................................................................................................. 15 1.1 Reminders on epoxy-amine chemistry....................................................................................................... 15 1.2 Transitions during network buildup ........................................................................................................... 16 1.2.1 Gelation ................................................................................................................................................. 16 1.2.2 Vitrification ............................................................................................................................................ 20 1.2.3 Influence of the stoichiometric ratio ..................................................................................................... 28 1.3 Topological homogeneity of the network .................................................................................................. 32 1.4 CPM-filled epoxy networks ........................................................................................................................ 34 2 Technologies to synthesize polymer microparticles ..................................................................................... 41 2.1 Overview of synthesis techniques .............................................................................................................. 41 2.2 Precipitation polymerization ...................................................................................................................... 43 2.2.1 Principle of the reaction-induced phase separation (RIPS) phenomenon ............................................. 44 2.2.2 Synthesis of CPMs via free radical polymerization ................................................................................ 46 2.2.3 Synthesis of CPM via polyaddition polymerization ................................................................................ 48 2.3 Conclusions ................................................................................................................................................ 51 II Synthesis and characterization of epoxy-based cross-linked polymer microparticles (CPMs) via precipitation polymerization ..................................................... 53 1 Introduction ................................................................................................................................................ 53 2 Experimental ............................................................................................................................................... 54 2.1 Materials .................................................................................................................................................... 54 2.2 Synthesis protocol ...................................................................................................................................... 54 2.3 Characterization techniques ...................................................................................................................... 55 3 Results and discussion ................................................................................................................................. 57 3.1 Synthesis and characterization of the reference CPMs ............................................................................. 57 3.1.1 Monitoring of the CPM synthesis .......................................................................................................... 57 Cette thèse est accessible à l'adresse : http://theses.insa-lyon.fr/publication/2014ISAL0018/these.pdf © [M.L. Michon], [2014], INSA de Lyon, tous droits réservés 3.1.2 Characterization of the CPMs ................................................................................................................ 62 3.2 Influence of the stoichiometric ratio ......................................................................................................... 68 3.2.1 Time to phase separation ...................................................................................................................... 68 3.2.2 Thermal properties ................................................................................................................................ 69 3.2.3 Composition of the CPMs by elemental analysis ................................................................................... 70 3.2.4 Composition by NIR spectroscopy ......................................................................................................... 71 3.2.5 Morphology ........................................................................................................................................... 71 3.2.6 Conclusion.............................................................................................................................................. 72 3.3 Influence of the reaction time ................................................................................................................... 72 3.4 Influence of the monomer structure ......................................................................................................... 73 3.4.1 Use of an aliphatic amine ...................................................................................................................... 74 3.4.2 Use of a higher molar mass DGEBA ....................................................................................................... 75 3.4.3 Conclusion.............................................................................................................................................. 77 4 Conclusions ................................................................................................................................................. 78 III CPMs as reactive fillers: quantification of the amine functionnality .................... 79 1 Introduction ................................................................................................................................................ 79 2 Literature review on titration techniques .................................................................................................... 80 2.1 Amine titration by fluorescent labeling ..................................................................................................... 80 2.2 Acid/Base titration ..................................................................................................................................... 83 2.3 Amine titration with SPDP .......................................................................................................................... 83 2.4 Amine titration with sulpho-SHPP ............................................................................................................. 84 2.5 Amine titration with ninhydrin .................................................................................................................. 85 3 Experimental ............................................................................................................................................... 88 3.1 Grafting of a fluorescent dye ..................................................................................................................... 88 3.1.1 Selection of the fluorescent dye and synthesis protocol ....................................................................... 88 3.1.2 Protocol for the grafting of the dye ....................................................................................................... 89 3.2 Amine titration with ninhydrin .................................................................................................................. 90 3.2.1 Protocol for qualitative test ................................................................................................................... 90 3.2.2 Protocol for quantitative tests ............................................................................................................... 90 3.3 Amine reactivity by differential scanning calorimetry (DSC) ..................................................................... 93 3.4 Monitoring of CPM reactivity towards DGEBA by Near-Infrared spectroscopy......................................... 93 4 Results on surface amine titration ............................................................................................................... 94 4.1 Theoretical calculation of surface amine of CPMs ..................................................................................... 94 Marie-Laure Michon, IMP@INSA, 2014 Cette thèse est accessible à l'adresse : http://theses.insa-lyon.fr/publication/2014ISAL0018/these.pdf © [M.L. Michon], [2014], INSA de Lyon, to us droits réservés Page 8 4.2 Qualitative titration test............................................................................................................................. 97 4.3 Quantitative measurements of amino groups on CPM surface ................................................................. 99 4.3.1 Titration of primary and secondary amine with a fluorescent probe: semi-quantification .................. 99 4.3.2 Titration of primary and secondary amine with ninhydrin .................................................................. 102 4.4 Conclusions .............................................................................................................................................. 105 5 Amine reactivity of CPMs towards epoxy systems ..................................................................................... 107 5.1 Amine reactivity of CPMs towards DER 331 by DSC ................................................................................ 107 5.2 Amine reactivity of CPMs towards DER 331 by NIR ................................................................................. 112 6 Conclusion ................................................................................................................................................. 114 IV Contribution of CPMs in an epoxy-amine network – Influence of the process115 1 Introduction .............................................................................................................................................. 115 2 Experimental ............................................................................................................................................. 115 2.1 Materials .................................................................................................................................................. 115 2.2 Processes in the manufacture of CPM-filled epoxy networks ................................................................. 116 2.2.1 CPM epoxy networks from the dispersion of CPMs in DGEBA ............................................................ 116 2.2.2 CPM epoxy networks from the solvent-assisted dispersion of CPMs in tetrahydrofuran and DGEBA 117 2.2.3 CPM epoxy networks from the dispersion of CPMs in IPD .................................................................. 117 2.3 Protocol for the investigation of the diffusion of monomers into the CPM core .................................... 118 2.3.1 Diffusion of a fluorescent probe into the CPM core in the presence of tetrahydrofurane ................. 118 2.3.2 CPM-filled epoxy-amine network with the use of a brominated epoxy prepolymer .......................... 119 2.4 Characterization techniques .................................................................................................................... 120 2.4.1 DSC ....................................................................................................................................................... 120 2.4.2 Chemorheology experiments .............................................................................................................. 121 2.4.3 Near-infrared (NIR) spectroscopy ........................................................................................................ 121 2.4.4 Scanning electron microscopy (SEM) ................................................................................................... 124 2.4.5 Dynamical mechanical analysis (DMA) ................................................................................................ 124 3 Results and discussion ............................................................................................................................... 125 3.1 CPM epoxy networks from the dispersion of CPMs in DGEBA................................................................. 125 3.1.1 Stability of the CPM-DGEBA dispersion ............................................................................................... 125 3.1.2 DSC investigation ................................................................................................................................. 126 3.1.3 Chemorheology.................................................................................................................................... 132 3.1.4 Kinetics by NIR spectroscopy ............................................................................................................... 135 3.1.5 Conversion after isothermal curing ..................................................................................................... 138 Marie-Laure Michon, IMP@INSA, 2014 Cette thèse est accessible à l'adresse : http://theses.insa-lyon.fr/publication/2014ISAL0018/these.pdf © [M.L. Michon], [2014], INSA de Lyon, to us droits réservés Page 9