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Direct Utilization of Elemental Sulfur for Novel Copolymeric Materials Direct Utilization Of Elemental Sulfur For Novel Copolymeric Materials Item Type text; Electronic Dissertation Authors Griebel, Jared James Publisher The University of Arizona. Rights Copyright © is held by the author. Digital access to this material is made possible by the University Libraries, University of Arizona. Further transmission, reproduction or presentation (such as public display or performance) of protected items is prohibited except with permission of the author. Download date 11/10/2021 08:01:14 Link to Item http://hdl.handle.net/10150/556819 1 DIRECT UTILIZATION OF ELEMENTAL SULFUR FOR NOVEL COPOLYMERIC MATERIALS by Jared J. Griebel ____________________________ A Dissertation Submitted to the Faculty of the DEPARTMENT OF CHEMISTRY AND BIOCHEMISTRY In Partial Fulfillment of the Requirements For the Degree of DOCTOR OF PHILOSOPHY WITH A MAJOR IN CHEMISTRY In the Graduate College THE UNIVERSITY OF ARIZONA 2015 2 THE UNIVERSITY OF ARIZONA GRADUATE COLLEGE As members of the Dissertation Committee, we certify that we have read the dissertation prepared by Jared Griebel, entitled, “Direct Utilization of Elemental Sulfur for Novel Copolymeric Materials” and recommend that it be accepted as fulfilling the dissertation requirement for the Degree of Doctor of Philosophy. ___________________________________________________________ Date: 4/22/2015 Jeffrey Pyun ___________________________________________________________ Date: 4/22/2015 Richard Glass ___________________________________________________________ Date: 4/22/2015 Douglas Loy ___________________________________________________________ Date: 4/22/2015 Neal Armstrong Final approval and acceptance of this dissertation is contingent upon the candidate’s submission of the final copies of the dissertation to the Graduate College. I hereby certify that I have read this dissertation prepared under my direction and recommend that it be accepted as fulfilling the dissertation requirement. ___________________________________________________________ Date: 4/22/2015 Dissertation Director: Jeffrey Pyun 3 STATEMENT BY AUTHOR This dissertation has been submitted in partial fulfillment of the requirements for an advanced degree at the University of Arizona and is deposited in the University Library to be made available to borrowers under rules of the Library. Brief quotations from this dissertation are allowable without special permission, provided that an accurate acknowledgement of the source is made. Requests for permission for extended quotation from or reproduction of this manuscript in whole or in part may be granted by the head of the major department or the Dean of the Graduate College when in his or her judgment the proposed use of the material is in the interests of scholarship. In all other instances, however, permission must be obtained from the author. SIGNED: Jared J. Griebel 4 ACKNOWLEDGEMENTS The trials and tribulations I have experienced during the earning of this PhD have been many, but with the help of several amazing individuals I have succeed. However, I write these acknowledgements knowing that I cannot hope to properly thank everyone involved in my development as a chemist and as a person. I would first like to thank the members of my dissertation committee, Professor Richard Glass, Professor Douglas Loy, and Professor Neil Armstrong for taking the time to review this document. Each and every one of them has contributed greatly to my growth as a scientist and the combined knowledge the three of them possess is truly astounding and very inspiring for a young scientist. I would especially like to thank Professor Douglas Loy who graciously acted as a stand in PI during my first year as a graduate student, providing guidance and assistance as I acclimated to graduate school. I am truly indebted to my adviser, Professor Jeffrey Pyun, for being a true advocate in all of my scholarly pursuits; guiding me, coaching me, and sometimes correcting me to make for certain that I became a better scientist. No single person has toiled more in the past five years to ensure my success in the program and I am truly thankful for his commitment. Jeff was the entire reason I entered graduate school and attended the University of Arizona. He has given me so much, and I will continue to be indebted to him for every contribution I manage to make throughout my life. Throughout my time at University of Arizona I have had the opportunity to make several academic connections and collaborations all over the world. I am particularly indebted to Professor Robert Norwood and Soha Namnabat for their expertise in the field of Optical Science and their contributions to the work on developing novel polymeric materials for optics applications. To Dr. Michael Mackay and Ngoc Nguyen, who offered creative solutions for non- rheology inclined individuals and were extremely helpful in the fundamental thermomechanical and rheological characterization of our novel sulfur materials. And to Dr. Kookheon Char and Eui Tae Kim who were most helpful in colloid synthesis, copolymer formation with sulfur, and materials characterization. I have had the distinct pleasure of working with and mentoring undergraduate researchers John Ji, Kyle Arrington, Dominic Moronta, Laura Anderson, and high school student Rebecca Mulligan. Interacting with these eager individuals challenged me as a mentor and motivated me to be a better scientist. The assistance of Dominic Moronta and Laura Anderson was invaluable in aiding me in generating and characterizing the novel sulfur based materials. Both of these young scientists have bright futures and I look forward to seeing them excel in their fields. During my time at the University of Arizona, I have been surrounded by talented and motivated researchers within the Pyun group, and we have created an unusually collegial and friendly atmosphere in which to thrive. I would like to thank Dr. Bryan Korth, Dr. Pei Yuin Keng, Dr. Woo Jin Chung, Dr. Adam Simmonds, and Dr. Lawrence Hill who have each helped to train me as either an undergraduate or graduate student. I also greatly benefitted from discussions with Dr. Lawrence Hill, Philip Dirlam, Nicholas Pavlopoulos, and Tristan Kleine. We may be a small group but the ideas we generate and the research we conduct are world class 5 and no one compares to you four gentlemen. Thanks to Evan Jones and Stephanie Jenson for taking valuable time away from research to relax and have a cup of tea on a daily basis to really start the day off right. Thank you to my family and friends who were amazingly solid support throughout my time in graduate school. I cherished my visits to see them and the time I got to spend with them even if was for just a weekend. Because of them I had the drive to finish. Thank you especially to my parents, James and Julie, for the unconditional love and support and a helping hand, and sometimes wallet, when I really needed it most. Thank you to my in-laws Mark and Grace Svilar for the trust, love, and support that you provided Katherine and I, even from 2000 miles away. And thank you to my church family who have welcomed me in and made me feel so comfortable. They have given me a place to express myself and also to remove the burden that normally comes with the hustle and bustle of graduate school. And lastly, but most certainly not least I want to thank my beautiful, amazing, supportive wife, Katherine Griebel. I never thought you would move out to the desert to be with me but I am so happy you did. Life during graduate school has been hard but with you by my side it was bearable. Coming home to you at the end of the day made it all worthwhile. Your support means the world to me. I do everything I do and work as hard as I do for you, so that I can make you proud and we can start our lives together once I am finished. I look forward to our next milestone more than anything. I love you more than I can express in words. 6 TABLE OF CONTENTS ABSTRACT..................................................................................................................................10 CHAPTER 1: Polymerizations with Elemental Sulfur: A Novel Route to High Sulfur Content Polymer for Sustainability, Energy, and Defense......................................................17 1.1. Introduction..........................................................................................................17 1.2. Elemental Sulfur Production and Consumption...............................................19 1.3. High Sulfur-Content Materials...........................................................................22 1.3.1 Polymeric Sulfur........................................................................................22 1.3.2 Polysulfides................................................................................................25 1.3.2.1 Condensation Generated Copolymers............................................26 1.3.2.2 Free-Radically Generated Copolymers..........................................28 1.3.2.3 Ionically Generated Copolymers...................................................30 1.3.3 Sulfur and Sulfur-Composite Colloids.......................................................32 1.3.4 Novel Sulfur Allotropes and Macrocycles.................................................37 1.4. Challenges in Sulfur Chemistry and Processing...............................................40 1.5. Sulfur as an Unconventional Solvent and Reaction Medium..........................42 1.5.1 In-Situ Colloid Synthesis...........................................................................42
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