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Synthesis and Characterization of Vanillyl Alcohol Based Thermosetting Epoxy Resins

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Synthesis and Characterization of Vanillyl Alcohol Based Thermosetting Epoxy Resins Rowan University Rowan Digital Works Theses and Dissertations 8-18-2015 Synthesis and characterization of vanillyl alcohol based thermosetting epoxy resins Eric Hernandez Follow this and additional works at: https://rdw.rowan.edu/etd Part of the Chemical Engineering Commons Recommended Citation Hernandez, Eric, "Synthesis and characterization of vanillyl alcohol based thermosetting epoxy resins" (2015). Theses and Dissertations. 458. https://rdw.rowan.edu/etd/458 This Thesis is brought to you for free and open access by Rowan Digital Works. It has been accepted for inclusion in Theses and Dissertations by an authorized administrator of Rowan Digital Works. For more information, please contact [email protected]. SYNTHESIS AND CHARACTERIZATION OF VANILLYL ALCOHOL BASED THERMOSETTING EPOXY RESINS by Eric David Hernandez A Thesis Submitted to the Department of Chemical Engineering College of Engineering In partial fulfilment of the requirement For the degree of Master of Science in Chemical Engineering at Rowan University July 31, 2015 Thesis Chair: Joseph F. Stanzione, III, Ph.D. © 2015 Eric D. Hernandez Dedication For mom Acknowledgements I would like to offer my sincerest gratitude to Dr. Joseph F. Stanzione, III, who has served as my graduate thesis advisor over the past two years. Dr. Stanzione has been both a knowledgeable and encouraging mentor who has provided me with instrumental guidance and direction throughout the course of this research. I am truly grateful to have had the opportunity to have worked with him. In addition, he has provided me with multiple opportunities to attend conferences and workshops and travel to places I had never before been, including Denver, CO and Washington, DC. He has helped me to network with fellow scientists and engineers and has even afforded me the opportunity to work with some of his colleagues. Dr. Stanzione’s keen optimism and support undoubtedly aided me in staying positive when I encountered research roadblocks, and without him this thesis would not have been possible. I would like to recognize my fellow lab mates and the graduate students who shared an office with me. I would also like to thank Dr. John La Scala and Dr. Joshua Sadler of the Army Research Laboratory for providing me the opportunity to collaborate with them. I would like to acknowledge the late Dr. Richard Wool and Kaleigh Reno of the University of Delaware for the opportunity to collaborate with them as well. In addition, I would like to express gratitude to the Army Research Laboratory for their generous support and funding via Cooperative Agreement W911NF-14-2-0086. Finally, I would like to thank my family and friends who have been supportive of my goals and career path. Most especially, I would like to thank my mother, Patricia Fabrizio, who has been there for me every step of the way throughout my entire life. She is my inspiration and I am truly indebted to her. iv Abstract Eric D. Hernandez SYNTHESIS AND CHARACTERIZATION OF VANILLYL ALCOHOL BASED THERMOSETTING EPOXY RESINS 2014-2015 Joseph F. Stanzione, III, Ph. D. Master of Science in Chemical Engineering Lignin is a natural and abundant renewable material composed of crosslinked phenylpropenyl units that when strategically depolymerized could potentially yield renewable bio-based aromatic building blocks for applications in high-performance thermosetting epoxy resins. Vanillyl alcohol, a lignin derived aromatic diol, is a potential platform chemical for the production of renewable bisphenols and epoxy thermosets. A new bio-based bisphenol (bisguaiacol) was synthesized via electrophilic aromatic condensation of vanillyl alcohol and guaiacol, from which diglycidyl ether of bisguaiacol (DGEBG) was prepared via epoxidation with epichlorohydrin. The thermomechanical properties of DGEBG blended with a commercial BPA-based epoxy resin and cured with a diamine were investigated via dynamic mechanical analysis (DMA). In addition, two bio- based diepoxy monomers were synthesized from vanillyl alcohol (DGEVA) and gastrodigenin (DGEGD) and characterized via 1H-NMR, 13C-NMR, FTIR, MS, and GPC. Vanillyl alcohol based epoxy resins bear a methoxy group covalently bonded to the aromatic ring ortho to the glycidyl ether group. The thermomechanical properties of cured DGEVA and DGEGD thermosets were compared to those of the cured DGEBG and commercially available thermosets to determine the effect of the methoxy moiety. DMA results indicate that the presence of the methoxy lowers the glass transition temperature (Tg), yet increases the storage modulus (E′) at 25 °C in cured epoxy-amine systems. v Table of Contents Abstract ............................................................................................................................... v List of Figures .................................................................................................................. viii List of Tables ..................................................................................................................... xi Chapter 1: Introduction ....................................................................................................... 1 1.1 Overview and Organization .................................................................................... 1 1.2 Introduction to Thermosetting Epoxy Resins ......................................................... 2 1.3 Bisphenols ............................................................................................................... 3 1.4 Epichlorohydrin ...................................................................................................... 7 1.5 Synthesis of Diglycidyl Ethers.............................................................................. 10 1.6 Epoxy Curing ........................................................................................................ 15 1.7 Bio-based Epoxy Resins ....................................................................................... 16 1.8 Lignin .................................................................................................................... 17 1.9 Vanillin ................................................................................................................. 22 Chapter 2: Characterization Methods ............................................................................... 28 2.1 Introduction ........................................................................................................... 28 2.2 Nuclear Magnetic Resonance (NMR) Spectroscopy ............................................ 28 2.3 Fourier Transform Infrared (FTIR) Spectroscopy ................................................ 33 2.4 Gel Permeation Chromatography (GPC) .............................................................. 36 2.5 Dynamic Mechanical Analysis (DMA) ................................................................ 37 Chapter 3: Experimental Materials and Methods ............................................................. 40 3.1 Introduction ........................................................................................................... 40 3.2 Materials ............................................................................................................... 40 3.3 Synthesis of Bisguaiacol ....................................................................................... 41 3.4 Synthesis of Diglycidyl Ether of Bisguaiacol (DGEBG) ..................................... 42 vi Table of Contents (Continued) 3.5 Synthesis of Diglycidyl Ether of Vanillyl Alcohol (DGEVA) ............................. 44 3.6 Synthesis of Diglycidyl Ether of Gastrodigenin (DGEDG) ................................. 46 3.7 Characterization of Monomers ............................................................................. 48 3.8 Extent of Cure ....................................................................................................... 50 3.9 Polymer Properties ................................................................................................ 52 Chapter 4: Results and Discussion .................................................................................... 54 4.1 Introduction ........................................................................................................... 54 4.2 Synthesis of Bisguaiacol ....................................................................................... 56 4.3 Synthesis and Characterization of Epoxy Pre-polymers ....................................... 62 4.4 Synthesis of Epoxy-Amine Systems and Extent of Cure...................................... 66 4.5 Effect of Methoxy Group on Epoxy-Amine Polymer Properties ......................... 69 4.6 Properties of DGEBG Polymer Blend .................................................................. 75 Chapter 5: Conclusions and Recommendations for Future Work .................................... 78 5.1 Conclusions ........................................................................................................... 78 5.2 Recommendations for Future Work...................................................................... 79 References ......................................................................................................................... 83 Appendix A: 1H and 13C NMR Spectra ............................................................................ 89 Appendix B: Mass Spectrometry Spectra ....................................................................... 101 Appendix
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