Wayne State University Wayne State University Dissertations 1-1-2016 Synthesis, Characterization, And Properties Of Peroxo-Based Oxygen-Rich Compounds For Potential Use As Greener High Energy Density Materials Nipuni-Dhanesha Horadugoda Gamage Wayne State University, Follow this and additional works at: http://digitalcommons.wayne.edu/oa_dissertations Part of the Oil, Gas, and Energy Commons, and the Organic Chemistry Commons Recommended Citation Gamage, Nipuni-Dhanesha Horadugoda, "Synthesis, Characterization, And Properties Of Peroxo-Based Oxygen-Rich Compounds For Potential Use As Greener High Energy Density Materials" (2016). Wayne State University Dissertations. Paper 1372. This Open Access Dissertation is brought to you for free and open access by DigitalCommons@WayneState. It has been accepted for inclusion in Wayne State University Dissertations by an authorized administrator of DigitalCommons@WayneState. SYNTHESIS, CHARACTERIZATION, AND PROPERTIES OF PEROXO-BASED OXYGEN-RICH COMPOUNDS FOR POTENTIAL USE AS GREENER HIGH ENERGY DENSITY MATERIALS by NIPUNI-DHANESHA HORADUGODA GAMAGE DISSERTATION Submitted to the Graduate School of Wayne State University, Detroit, Michigan in partial fulfillment of the requirements for the degree of DOCTOR OF PHILOSOPHY 2015 MAJOR: CHEMISTRY (Inorganic) Approved By: Advisor Date © COPYRIGHT BY NIPUNI-DHANESHA HORADUGODA GAMAGE 2015 All Rights Reserved DEDICATION To my parents, husband, and son The people who have always supported me, helped me to rise up whenever I fell, and encouraged and inspired me to accomplish my goals. ii ACKNOWLEDGMENTS I would like to express my sincere gratitude to Professor Charles H. Winter for taking me into Winter lab, which was similar to a second home for me throughout the phD program. His guidance and support as my advisor at Wayne State University allowed me to progress rapidly and successfully. I have obtained numerous synthetic, technical, writing, and presentation skills that are invaluable for my future career while I was in Winter lab. I am also indebted to Professor Charles H. Winter for the confidence that he built in me to push forward by encouraging me all throughout. I am extremely grateful for the wonderful collaboration we had with Prof. Thomas M. Klapötke, Ludwig-Maximilians University, Munich, Germany. The syntheses and standard sensitivity measurements carried out by Benedikt Stiasny and the energetic performance calculations carried out by Dr. Jörg Stierstorfer have completed the research study of peroxo-based compounds for my PhD. I greatly appreciate their hard work and time spent on research, discussions via e-mail, and preparation of manuscripts. I am grateful to my committee members, Prof. James H. Rigby, Dr. Stanislav Groysman, and Dr. Charles L. Dezelah, for their valuable comments and suggestions on my dissertation. I thank Dr. Stanislav Groysman also for allowing me to use the IR spectrometer in his lab. It was a great pleasure to work with the crystallography expert Dr. Philip D. Martin as he was extremely nice to me whenever I brought down a crystal to place in the diffractometer. I am grateful for all the X-ray crystal structures he solved and for his assistance with cif files in the preparation of manuscripts. I would also like to thank Dr. iii Bashar Ksebati and Dr. Yuriy Danylyuk for assisting me with NMR and mass spectrometry, respectively. I am thankful to Nestor Ocampo for his support on software or hardware issues. I appreciate the assistance of the science stores and the non- academic staff members in various ways throughout the PhD program. I would like to pay my gratitude to the past and present Winter lab members who were there while I was in the PhD program for the friendly working environment. I was happy to get involved in all the long chemistry discussions we had, especially with Joseph P. Klesko. Groysman, Brock, and Verani lab members were also always willing to assist me whenever I was in need and I am sincerely grateful for all of their support and friendship. I am extremely fortunate to have two wonderful parents who have dedicated their life for me and my siblings and I am unable to express my gratitude in words for all they have done for me. I am what I am today because of my loving parents. My husband, G. H. Layan Savithra has been the man in my life who protected, cared for, and supported me for more than a decade. The B.S. special degree program in chemistry of University of Colombo was an intense program that brought us together and we were able to push through the hard work ending up as the two top students of our batch. Not only had I learned to love chemistry, but also my path towards PhD in chemistry was opened up because of Layan who was an extremely talented student. I am extremely grateful for all he has done. Last but not least my son, Senuk Y. Savithra is the greatest inspiration I have that keeps me pushing forward no matter what comes in the way. iv TABLE OF CONTENTS DEDICATION .................................................................................................................ii ACKNOWLEDGMENTS ............................................................................................... iii LIST OF TABLES ....................................................................................................... viii LIST OF FIGURES ........................................................................................................xi LIST OF SCHEMES .................................................................................................... xvi LIST OF ABBREVIATIONS ....................................................................................... xvii CHAPTER 1 – Introduction ......................................................................................... 1 1.1 High Energy Density Materials (HEDMs) ................................................. 1 1.2 Deflagration and Detonation .................................................................... 5 1.3 Design of HEDMs .................................................................................... 7 1.4 Sensitivity and Energetic Performance Tests and Calculations ............. 12 1.5 Peroxo-Based Oxygen-Rich Compounds for Use as Greener HEDMs .. 15 1.6 Thesis Problem ...................................................................................... 37 CHAPTER 2 – Synthesis, Characterization, and Study of the Sensitivities and Energetic Properties of tert -Butyl Peroxides ..................................... 39 2.1 Introduction ............................................................................................ 39 2.2 Results and Discussion .......................................................................... 42 2.3 Conclusion ............................................................................................. 59 2.4 Experimental Section ............................................................................. 60 CHAPTER 3 – Synthesis, Characterization, and Study of Surprisingly Highly Energetic and Low Sensitivity tert -Butyl Peroxy Esters with Low Oxygen and Nitrogen Contents ............................................................ 69 v 3.1 Introduction ............................................................................................ 69 3.2 Results and Discussion .......................................................................... 72 3.3 Conclusion ............................................................................................. 99 3.4 Experimental Section ............................................................................ 100 CHAPTER 4 – Synthesis, Characterization, and Study of Oxygen-Rich Geminal Hydroperoxides with Impressive Detonation Performances and Practically Useful Sensitivities ........................................................... 108 4.1 Introduction ........................................................................................... 108 4.2 Results and Discussion ......................................................................... 111 4.3 Conclusion ............................................................................................ 136 4.4 Experimental Section ............................................................................ 137 CHAPTER 5 − Tuning the Impact and Friction Sensitivities and Energetic Performances of a Series of Well-Characterized Cyclic Hydroperoxy Compounds ................................................................... 148 5.1 Introduction ........................................................................................... 148 5.2 Results and Discussion ......................................................................... 152 5.3 Conclusion ............................................................................................ 190 5.4 Experimental Section ............................................................................ 191 CHAPTER 6 − Synthesis, Characterization, and Study of Highly Energetic Peroxy Acids with Surprisingly Low Impact and Friction Sensitivities ............................................................................................ 201 6.1 Introduction ........................................................................................... 201 6.2 Results and Discussion ......................................................................... 204 vi 6.3 Conclusion ............................................................................................ 225 6.4 Experimental Section ...........................................................................