Development of monomers for production of high performance paints Joana Vieira de Freitas Barbosa Dissertation presented for the degree of Doctor in Chemical and Biological Engineering by the University of Porto Supervisors Margarida M.S.M. Bastos, Auxiliar Professor Co-Supervisors Adélio Miguel Magalhães Mendes, Associated Professor Fernão Domingos de Magalhães, Auxiliar Professor LEPAE - Laboratory of Engineering Processes, Environment and Engineering Chemical Engineering Department Faculty of Engineering – University of Porto Porto, 2013 Acknowledgments I would like to acknowledge to Portuguese Foundation for Science and Technology (FCT) for my Ph.D. grant (SFRH/BDE/15623/2006), CIN-Corporação Industrial do Norte and Resiquímica S.A. for providing financial support. My sincere thanks to my supervisors Professor Margarida Bastos, Professor Fernão Magalhães and Professor Adélio Mendes for making this project possible, providing me scientific and technological knowledge. I also thank you, for giving me the opportunity to do this work, believing in me and in my capabilities. A word of gratitude also goes to ARCP-Association Competence Network in Polymers, for giving the necessary resources to conduct this work, and an especially thanks to Sarah and Eva who always tried to solve problems that arise. I would like to thank my colleagues from E201, specially, Joana (for the sympathy, support, for sharing knowledge, the “hotte” and “fats”), Berta, Salomé, Rui, Elisabete, Maria and Maria João for helping me with my work, and all my colleagues from E108 for the support. An especially thanks to Ângela Daniela and Joana Fidalgo, for the support and for sharing with me the good and bad moments and to Ratola, for all the good talks and advices. I would like to express my gratitude to the Chemical Engineering Department at FEUP, LEPAE-Laboratory for Process, Environmental and Energy Engineering. Thanks to Fátima, Sr. Serafim, Arminda, Sónia, Zé Luís and Luís Martins. I would like to thank D. Fátima, D. Maria José and Joana Azeredo for their help with secretary work. I am very thankful to Mariana Andrade from Materials Center of the University of Porto (CEMUP), for her support during data processing of many nuclear magnetic resonance spectra. My gratitude goes to my family: my parents who show me the real values and principles that I intend to follow throughout my life. An especial thanks to my Mom and my Brother (my best big brother) for all the love, support, advices, encouragement, and trust…who have always believed in me! Without you this would never have been possible. Thanks to Ana, Maria and Inês for all the happiness and wonderful moments and, particular to the little girls for always make me smile. Thank to my cousin Teresa, for the support and for always being there for me. I am also grateful to my uncle Pinha for the laptop. An especial big kiss to my grandparents Zé, Avó Juju and Avó Pinha...you are always with me! Finally, to Pedro… Thank you for always being there, for your patience, support, comprehension and encouragement. To my son Afonso… Contents FIGURE CAPTIONS TABLE CAPTIONS NOMENCLATURE ABSTRACT RESUMO SOMMAIRE CHAPTER 1 ‐ Introduction .............................................................................................. 3 1.1. Vegetable oils ............................................................................................................ 6 1.1.1. Composition of vegetable oils ......................................................................... 6 1.1.2. Synthesis of derivatives from vegetable oils ................................................... 7 1.2. Polymerization ......................................................................................................... 13 1.2.1. Solvent polymerization ................................................................................. 15 1.2.2. Emulsion polymerization .............................................................................. 15 1.3. Paints ....................................................................................................................... 23 1.4. Dissertation outline .................................................................................................. 27 References ...................................................................................................................... 29 CHAPTER 2 - Synthesis and Characterization of Allyl Fatty Acid Derivatives as Reactive Coalescing Agents for Latexes ........................................................................ 37 Abstract ........................................................................................................................... 37 2.1. Introduction ............................................................................................................. 38 2.2. Experimental ............................................................................................................ 39 2.2.1. Materials ........................................................................................................ 39 2.2.2. Characterization Methods ............................................................................. 40 2.2.3. AFAD Synthesis ............................................................................................ 41 v 2.3. Results and Discussion ............................................................................................ 45 2.3.1. Synthesis Monitoring .................................................................................... 45 2.3.2. FT-IR characterization .................................................................................. 47 2.3.3. GC-FID and GC-MS characterization........................................................... 48 2.3.4. NMR spectroscopy ........................................................................................ 50 2.3.5. Film-forming behaviour ................................................................................ 52 2.3.6. Oxidative cure behaviour .............................................................................. 53 2.4. Conclusions ............................................................................................................. 56 Acknowledgments .......................................................................................................... 56 References ...................................................................................................................... 57 CHAPTER 3 - Synthesis and characterization of acrylic fatty acid derivative and use as reactive coalescing agent ................................................................................................ 63 Abstract ........................................................................................................................... 63 3.1. Introduction ............................................................................................................. 64 3.2. Experimental ............................................................................................................ 65 3.2.1. Materials ........................................................................................................ 65 3.2.2. Characterization methods .............................................................................. 65 3.2.3. AcFAD synthesis........................................................................................... 67 3.3. Results and discussion ............................................................................................. 67 3.3.1. Synthesis and AcFAD characterization by FT-IR......................................... 68 3.3.2. GC–MS characterization ............................................................................... 71 3.3.3. Characterization of AcFAD by NMR spectroscopy ..................................... 72 3.3.4. Film forming and oxidative cure performance .............................................. 78 3.4. Conclusions ............................................................................................................. 81 Acknowledgments .......................................................................................................... 81 References ...................................................................................................................... 82 vi CHAPTER 4 - Incorporation of an acrylic fatty acid derivative as comonomer for oxidative cure in an acrylic emulsion ............................................................................. 87 Abstract ........................................................................................................................... 87 4.1. Introduction ............................................................................................................. 88 4.2. Experimental ............................................................................................................ 89 4.2.1. Materials ........................................................................................................ 89 4.2.2. Characterization methods .............................................................................. 89 4.2.3. Solution polymerization of AcFAD .............................................................. 90 4.2.4. Emulsion copolymerization of AcFAD......................................................... 91 4.3. Results and discussion ............................................................................................. 93 4.3.1.