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Investigation on Oxygen-Rich Materials Based on Nitrocarbamates and Fox-7

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Investigation on Oxygen-Rich Materials Based on Nitrocarbamates and Fox-7 DISSERTATION ZUR ERLANGUNG DES DOKTORGRADES AN DER FAKULTÄT FÜR CHEMIE UND PHARMAZIE DER LUDWIG-MAXIMILIANS-UNIVERSITÄT MÜNCHEN INVESTIGATION ON OXYGEN-RICH MATERIALS BASED ON NITROCARBAMATES AND FOX-7 Quirin Josef Axthammer aus München, Deutschland 2016 ERKLÄRUNG Diese Dissertation wurde im Sinne von §7 der Promotionsordnung vom 28. November 2011 von Herrn Prof. Dr. T. M. Klapötke betreut. EIDESSTATTLICHE VERSICHERUNG Diese Dissertation wurde eigenständig und ohne unerlaubte Hilfe erarbeitet. München, den 03. Februar 2016 _______________________________ Quirin J. Axthammer Dissertation eingereicht am: 05.02.2016 1. Gutachter: Prof. Dr. T. M. Klapötke 2. Gutachter: Prof. Dr. K. Karaghiosoff Mündliche Prüfung: 29.02.2016 MEINER GELIEBTEN FAMILIE UND IM BESONDEREN MEINEN GROßVATER JOSEF MICHAEL AXTHAMMER * 03.11.1921 ✝ 13.03.2010 Danksagung Mein Dank gilt an vorderster Stelle meinem Doktorvater Prof. Dr. Thomas M. Klapötke für die die Aufnahme in den Arbeitskreis, die interessante Themenstellung, die stetige finanzielle und fachliche Unterstützung meiner Forschungsvorhaben sowie seine Begeisterung für die Wissenschaft. Herrn Prof. Dr. Konstantin Karaghiosoff danke ich nicht nur für die freundliche Übernahme des Zweitgutachtens dieser Dissertation, sondern auch für die Einarbeitung in die Kristallographie und deren Faszination dafür, die ich nun mehr als nur nachvollziehen kann. Der Prüfungskommission, bestehend aus Prof. Dr. T. M. Klapötke, Prof. Dr. K. Karaghiosoff, Prof. Dr. F. Bracher, Prof. Dr. J. Evers, Prof. Dr. Beck und Prof. Dr. A. Kornath, danke ich für Ihre Zeit und der Bereitschaft zur Bildung der selbigen. Die Erstellung dieser Arbeit wurde durch ein Promotionsstipendium der Hanns-Seidel-Stiftung gefördert. Mein Dank richtet sich daher an die Hanns-Seidel-Stiftung für die finanzielle, aber auch für die ideelle Förderung. Im Besonderen werden mir die tollen Besuche und Seminare in Wildbad Kreuth und Kloster Banz im Gedächtnis bleiben. Vielen Dank dafür! Herrn Dr. Burkhard Krumm danke ich für die gute Betreuung, den zahllosen Anregungen, Diskussionen und Hilfestellungen sowie für die Aufnahme zahlreicher NMR Spektren. Des Weiteren möchte ich Ihm für die immer sehr akribische Korrektur jeglicher Schriftstücke danken. Dr. Jörg Stierstorfer danke ich für Hilfestellungen und Anregungen aller Art, sowie seinen teambildenden Maßnahmen im Arbeitskreis. Frau Irene Scheckenbach danke ich für Ihr organisatorisches Multitalent und Ihre Unterstützung in verschiedensten und alltäglichen bürokratischen Aufgaben. Dr. Sebastian F. Rest und Dr. Richard Moll danke ich für die Einführung in die nicht immer einfache Chemie der hochenergetischen Materialien und ihre psychologische Unterstützung bei einigen Geräuscherscheinungen. Allen während meiner Promotion anwesenden Laborkollegen im Arbeitskreis danke ich für die stets sehr gute freundschaftliche Arbeitsatmosphäre. Besonderer Dank geht hier an alle Doktoranten des Labors D.3.100 Regina Scharf, Carolin Pflüger, Michael Weyrauther, Richard Moll, Sebastian Rest, Camilla Evangelisti und Thomas Reith, für alle fachlichen und weltanschaulichen Diskussionen. Regina Scharf und Carolin Pflüger danke ich für die Korrektur und für die besonders gute Zusammenarbeit jeweils in dem Bereich der hochenergetischen Treibstoff-Oxydatoren und im Bereich der Kristallographie. Besonderer Dank geht auch an all meine Praktikanten die alle mit viel Engagement einen erheblichen Beitrag zum Gelingen dieser Arbeit beigetragen haben. Meinen sehr lieben Freunden Max, Babsi, Sabine, Simone, Simon, Julia, Peter 2×, Katharina, Christian 2×, Susi, Stefan 2×, Marina, Berny, Eva, Florian, Kathi, Karl, Roland danke ich für Eure Unterstützung in der nicht immer sehr einfachen Zeit. Danke auch an all die großartigen Ablenkungen! Nicht zuletzt geht mein Dank an meine Familie, im Besonderen meinen Eltern Brigitte und Josef die mir durch Ihre unaufhörliche Unterstützung und Liebe dies alles erst ermöglicht haben. Meinen großartigen Schwestern Brigitte und Barbara danke ich dafür, dass ich mich immer auf Euch verlassen kann und Ihr mit Euren Familien (Mathias und Johanna, Tom und Gregor) ein einzigartiger Rückhalt seid. Table of Contents List of Schemes .................................................................................................... VI List of Figures ................................................................................................... VIII List of Tables ........................................................................................................ XI I General Introduction ............................................................................. 1 1 Classification of Energetic Materials .................................................................... 1 2 New Oxidizers for Solid Rocket Composite Propellants.................................. 4 3 The Chemistry of Carbamates and Nitrocarbamates ........................................ 8 4 Objective Target .................................................................................................... 10 5 References .............................................................................................................. 11 II Summary .............................................................................................. 13 1 The Nitrocarbamate of Trinitroethanol ............................................................. 14 2 Carbamates and Nitrocarbamates from Polynitro Alcohols........................... 14 3 The Polyvalent Nitrocarbamate of Pentaerythritol .......................................... 16 4 The Nitrocarbamate Relatives of Nitroglycerine and Co. ............................... 17 5 Nitrocarbamates of Polyvalent Sugar Alcohols ................................................ 18 6 The 1,1,1-Trinitroprop-2-yl Moiety .................................................................... 18 7 Michael Addition of Nitroform .......................................................................... 19 8 The 3,3,3-Trinitropropyl Unit ............................................................................. 20 9 New FOX-7 Derivatives ...................................................................................... 21 III Results and Discussion ....................................................................... 23 1 The Nitrocarbamate of Trinitroethanol .............................................. 25 1.1 Abstract .................................................................................................................. 26 1.2 Introduction ........................................................................................................... 26 1.3 Results and Discussion ......................................................................................... 27 1.3.1 Synthesis ................................................................................................. 27 1.3.2 NMR Spectroscopy............................................................................... 28 1.3.3 Single Crystal Structure Analysis ......................................................... 30 1.3.4 Vibrational Spectroscopy ..................................................................... 32 1.3.5 Thermal Stabilities and Energetic Properties .................................... 33 1.4 Conclusion ............................................................................................................. 36 1.5 Experimental Section ............................................................................................ 36 1.5.1 General Procedures .............................................................................. 36 I Table of Contents 1.5.2 Computational Details ......................................................................... 37 1.5.3 X-ray Crystallography .......................................................................... 38 1.5.4 Synthesis ................................................................................................ 38 1.6 References.............................................................................................................. 41 2 Carbamates and Nitrocarbamates from Polynitro Alcohols .............. 43 2.1 Abstract .................................................................................................................. 44 2.2 Introduction .......................................................................................................... 44 2.3 Results and Discussion ........................................................................................ 45 2.3.1 Synthesis and Characterization ........................................................... 45 2.3.2 NMR Spectroscopy .............................................................................. 46 2.3.3 Single Crystal X-ray Diffraction ......................................................... 47 2.3.4 Energetic Properties ............................................................................. 53 2.4 Conclusion ............................................................................................................. 54 2.5 Experimental Section ........................................................................................... 55 2.5.1 General Information ............................................................................ 55 2.5.2 X-ray Crystallography .......................................................................... 55 2.5.3 Energetic Properties and Computational Calculation ..................... 55 2.5.4 Synthesis
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