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Synthesis and Characterization of Deep Eutectic Solvents (Des) with Multifunctional Building Blocks

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Synthesis and Characterization of Deep Eutectic Solvents (Des) with Multifunctional Building Blocks SYNTHESIS AND CHARACTERIZATION OF DEEP EUTECTIC SOLVENTS (DES) WITH MULTIFUNCTIONAL BUILDING BLOCKS A Thesis Presented to The graduate faculty of the University of Akron In Partial Fulfillment of the Requirements of the Degree Master of Science Yi Ting Lo August, 2019 SYNTHESIS AND CHARACTERIZATION OF DEEP EUTECTIC SOLVENTS (DES) WITH MULTIFUNCTIONAL BUILDING BLOCKS Yi-Ting, Lo Thesis Approved: Accepted: _________________________ _________________________ Nicole Zacharia Department Chair Advisor Dr. Sadhan C. Jana ____________________________ _____________________________ Dr. Kevin Cavicchi Committee Member Interim Dean of the College Dr. Ali Dhinojwala ____________________________ _____________________________ Xiong Gong Dr. Dean of the Graduate School Committee Member Dr. Chand Midha _____________________________ Date ii ABSTRACT Ionic liquids have attracted interest as non-volatile liquids for numerous applications. An alternative material are deep eutectic solvent (DES) generated by mixing interacting crystalline species to generate a eutectic with a melting point below room temperature. In this thesis DESs were prepared by mixing quaternary ammonium compounds and diacids, which interact through hydrogen bonding. Mono- and di-functional quaternary ammonium compounds were either purchased or synthesized and mixed with different aliphatic dicarboxylic acids. The overarching goal of this work was to investigate DES formation from difunctional quaternary ammonium and dicarboxylic acid compounds to determine if polymeric-like DES could be obtained, with corresponding polymeric like properties (i.e. viscoelasticity, high viscosity, glass formation). Differential scanning calorimetry and optical microscopy were used to investigate the phase behavior of the different quaternary ammonium/acid pairs to determine the structural features that contribute to deep eutectic formation. iii ACKNOWLEDGEMENT I would like to express my sincere gratefulness to my advisor Professor Nicole Zacharia and Kevin Cavicchi for his constant guidance, encouragement and selfless support on my research. It is a great honor and pleasure for me to be a member of his group and to work as a graduate student under his instruction. I would like to acknowledge all my group members, especially Tzu Yu Lai for her kind help and suggestions on my work. My studies would not be completed without their help. I would like to thank Prof. Zacharia, Prof. Cavicchi and Prof. Xiong Gong for being my committee members. Lastly, I would express my deepest appreciation for my beloved my parents for their support throughout all these years that I have studied abroad. iv TABLE OF CONTENTS Page LIST OF TABLES………………………………………………………………………………….……………………viii LIST OF FIGURES…………………………………………………………………………….…………………………ix CHAPTER I. INTRODUCTION…….……………………………………………………………………….………………………1 1. Overview…………………………………………………………………………………………………………..1 1.1 Background……..………………………………………………………………..………………………..1 1.2 Traditional ionic liquids (ILs)…………………………….………………………………..…….….2 1.3 Deep eutectic solvents (DESs)………………………..……………………………………….…..3 1.4 Phase diagram…………………………………………………………………………………….………5 1.5 Eutectic point…………………………………………………………………..………………………….7 1.6 Types of DESs………………………………………………………..…………………..………………..7 1.7 Hole theory…………………………………………………………..………………………..…………..9 1.8 Properties of DESs………………………………………………………………………..……………10 1.9 Applications of DESs………………………………………………………………………….………16 2. Differential scanning calorimetry (DSC)…………………………………..……………….………22 v 3. Nuclear magnetic resonance spectroscopy (NMR)…………………..……………………..23 4. Polarized optical microscopy (POM)………………………………………………………………..24 II. Experiment I…………………….…………………………………………………..………………………….…25 1. Introduction……………………………………………………………………………..…………………….25 2. Experimental section………………………………………………………………..…………………….25 2.1 Materials………………………….………………………………………………….……………………25 2.2 Preparation of deep eutectic solvent………………………………………………..……….26 2.3 Illustration of phase diagrams…………………………………………………..……………….27 3. Result and discussion……………………………………………………………………………..……….27 3.1 Adipic acid + tetra-n-butylammonium bromide……………………………………..….28 4. Conclusion……………………………………………………………………………………………..……….31 III. Experiment II………………………………………………………………………………….……..…………..33 1. Introduction………………………………………………………………………………..………………….33 2. Experimental section………………………………………………………………………………..…….34 2.1 Materials………………………………………………………………………………………..…………34 2.2 Synthesis……………………………………………………………………………………….……..……35 2.3 Characterization……………………………………………………………………..…………………39 3. Result and discussion…………………………………………………………………..………………….43 3.1 Visual observation…………………………………………….……………………..……….………44 vi 3.2 Polarized optical microscopy (POM)…………………….…………………..……….………46 3.3 1H NMR…………………………………………………………………………………………….....……47 3.4 Differential scanning calorimetry (DSC)………………………………………..……………53 IV. Conclusion……………………………………………………………………………………..………..……….58 REFERENCES…………………………………………………………………….……………………………………..59 vii LIST OF TABLES Tables Page 1.1 General Formula for the Classification of DESs[3]…………………….…………………….…….8 2.1 Melting points of products with different ratio of materials…………..…………….……30 viii LIST OF FIGURES Figure Page 1.1 Material and synthesis process of deep eutectic solvents[13]……………………………….2 1.2 Typical structures of the hydrogen bond donors and acceptors[2]………………………..4 1.3 Optimized conformation of hydrogen bonding between HBD and HBA in deep eutectic solvent[1]………………………………………………………………………………………………..5 1.4 Schematic representation of a eutectic point of binary eutectic system[3]……………6 1.5 Freezing points of choline chloride with five carboxylic acids[2]…………………………12 1.6 Relationship between viscosity and temperature of multiple types of different kinds of DESs[13]…………………………………………………………………………………………………14 1.7 Densities of the glycerol/ChCl DES as a function of the molar ratio[2]………………..16 1.8 The correlation between the CO2 adsorption of polyDEM and pressure[1]…………18 1.9 Glycerol mole fraction in an AcChCl–glycerol mixture in contact with biodiesel containing glycerol as a function of time[2]………………………………………………………..20 1.10 Material under normal microscopy………………………………………………………………….24 1.11 Material under polarized microscopy………………………………………………………………24 2.1 Structure of adipic acid……………………………………………………………………………………..26 ix 2.2 Structure of Tetra-n-butylammonium bromide………………………………………………….26 2.3 Photo of Pyris DSC8500 machine………………………………………………………………………27 2.4 DSC figures from 0-50% mole percentage of adipic acid……………………………………28 2.5 DSC figures from 0-50% mole percentage of adipic acid……………………………………29 2.6 Phase diagram of DES composed of adipic acid and tetra-n-butylammonium bromide…………………………………………………………………………………………………………….30 2.7 Freezing points of choline chloride with five carboxylic acids[2]…………………………32 3.1 Structure of adipic acid……………………………………………………………………………………..34 3.2 Structure of succinic acid…………………………………………………………………………………..34 3.3 Structure of dodecanedioic acid………………………………………………………………………..34 3.4 Structure of (Br-Ph-(N(Bu)3)2)…………………………………………………………………………….35 3.5 Structure of (Br-Ph-(N(Oct)3)2)…………………………………………………………………………..35 3.6 Photo of (Br-Ph-(N(Bu)3)2)………………………………………………………………………………….36 3.7 NMR figure of (Br-Ph-(N(Bu)3)2)…………………………………………………………………………37 3.8 Photo of (Br-Ph-(N(Oct)3)2)………………………………………………………………………………..38 3.9 NMR figure of (Br-Ph-(N(Oct)3)2)……………………………………………………………………….38 3.10 Schematic representation of a eutectic point of binary eutectic system[3]……….44 3.11 State of 45 mole% adipic acid and 55 mole% (Br-Ph-(N(Bu)3)2) at initial………….45 3.12 State of 45 mole% adipic acid and 55 mole% (Br-Ph-(N(Bu)3)2) after 1 hour…….45 x 3.13 State of 45 mole% adipic acid and 55 mole% (Br-Ph-(N(Bu)3)2) after 2 hours…..45 3.14 POM figure of 50 mole% adipic acid+50 mole% (Br-Ph-(N(Bu)3)2)……………………46 3.15 POM figure of 60 mole% adipic acid+40 mole% (Br-Ph-(N(Bu)3)2)……………………46 3.16 POM figure of 50 mole% adipic acid+50 mole% (Br-Ph-(N(Oct)3)2)…………………..47 3.17 POM figure of 50 mole% adipic acid+50 mole% (Br-Ph-(N(Oct)3)2)…………………..47 3.18 NMR figure of (Br-Ph-(N(Bu)3)2)……………………………………………………………………….47 3.19 NMR figure of (Br-Ph-(N(Oct)3)2)……………………………………………………………………..48 3.20 NMR figure of adipic acid………………………………………………………………………………..48 3.21 NMR figure of succinic acid……………………………………………………………………………..48 3.22 NMR figure of dodecanedioic acid…………………………………………………………………..49 3.23 NMR figure of 40 mole% adipic acid + 60 mole% (Br-Ph-(N(Bu)3)2…………………..49 3.24 NMR figure of 50 mole% adipic acid + 50 mole% (Br-Ph-(N(Bu)3)2……………………49 3.25 NMR figure of 60 mole% adipic acid + 40 mole% (Br-Ph-(N(Bu)3)2……………………50 3.26 NMR figure of 40 mole% succinic acid + 60 mole% (Br-Ph-(N(Bu)3)2………………..50 3.27 NMR figure of 50 mole% succinic acid + 50 mole% (Br-Ph-(N(Bu)3)2………………..51 3.28 NMR figure of 60 mole% succinic acid + 40 mole% (Br-Ph-(N(Bu)3)2………………..51 3.29 NMR figure of 50 mole% dodecanedioic acid + 50 mole% (Br-Ph-(N(Bu)3)2……..51 3.30 NMR figure of 70 mole% dodecanedioic acid + 30 mole% (Br-Ph-N(Oct)3)2……..52 3.31 DSC figure of adipic acid+(Br-Ph-(N(Bu)3)2) (endo up)………………………………………53 xi 3.32 DSC figure of succinic acid+(Br-Ph-(N(Bu)3)2) (endo down)………………………………54 3.33 DSC figure of dodecanedioic acid+(Br-Ph-(N(Bu)3)2) (endo down)……………………54 3.34 DSC figure of adipic acid+(Br-Ph-(N(Oct)3)2) (endo up)…………………………………….55 3.35 DSC figure of succinic acid+(Br-Ph-(N(Oct)3)2) (endo down)…………………………….55 3.36 DSC figure of dodecanedioic acid+(Br-Ph-(N(Oct)3)2) (endo down)………………….56 3.37 XRD figure of the material and the DES product………………………………………………57 xii CHAPTER
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