Energetic Materials based on Isocyanuric acid and 1,2,4-Oxadiazole Derivatives

327 Pages·2013·17.09 MB·English

by  Norbert Mayr

Dissertation zur Erlangung des Doktorgrades
der Fakultät für Chemie und Pharmazie
der Ludwig-Maximilians-Universität München

Energetic Materials based on
Isocyanuric acid and 1,2,4-Oxadiazole
Derivatives
-
Synthesis and Characterization

Norbert Thorsten Mayr
aus
Dillingen an der Donau
(Deutschland)

2013
Introduction

ii
Introduction
Erklärung
Diese Dissertation wurde im Sinne von § 7 der Promotionsordnung vom 28.
November 2011 von Herrn Prof. Dr. Thomas M. Klapötke betreut.

Eidesstattliche Versicherung
Diese Dissertation wurde eigenständig und ohne unerlaubte Hilfe erarbeitet.

München 25. Februar 2013

Norbert Mayr

Dissertation eingereicht am
1. Gutachter Prof. Dr. Thomas M. Klapötke
2. Gutachter Prof. Dr. Konstantin Karaghiosoff
Mündliche Prüfung 21. März 2013

iii
Introduction

“If something comes to life in others because of you,
then you have made an approach to immortality. “

Norman Cousins (* 24. Juni 1915; † 30. November 1990)

Für meine Familie und alle lieben Menschen,
die den Weg mit mir bis hier gegangen sind.

iv
Introduction
Danksagung
Zuerst möchte ich mich bei meinem Doktorvater Prof. Dr. Thomas M. Klapötke
bedanken, nicht nur für die Möglichkeit der Dissertation sondern vor allem für seine
Unterstützung in dieser Zeit, für die Inspiration, das Vertrauen und die Offenheit
gegenüber ungewöhnlichen Ansätzen.
Meinem Zweitgutachter Prof. Dr. Konstantin Karaghiosoff möchte ich für sein
freundliche väterliche Unterstützung und die viele fruchtbare Diskussionen nicht nur
über Chemie bedanken.
Bei Frau Irene Scheckenbach, die gute Seele des Arbeitskreises, bedanke ich mich für
Ihre unendliche Unterstützung bei organisatorischen und bürokratischen
Unwegbarkeiten an der LMU.
Bei Dr. Jörg Stierstorfer bedanke ich mich für seine schier grenzenlose Energie und viel
Motivation.
Dr. Franz Martin und Dr. Marianne Rotter danke ich für ihre Ehrlichkeit, ihr Vertrauen
und Ihre Freundschaft.
Meinen Laborkollegen Sebastian Rest, Richard Moll, Dr. Karina Tarantik und Dr. Xaver
Steemann danke für viele Jahre voll Freude, chemischer Genialität, jede Menge
schlechte Kalauer und endlosen Stunden Rock Antenne und Helge Schneider.
Ich könnte jetzt viele nennen die Ihren Weg mit mir begonnen und längst ihr Weg
gemacht haben aber besonders stolz bin ich die folgenden Menschen kennengelernt
haben zu dürfen: Dr. Richard Betz, Dr. Stefan Sproll, Dr. Hendrik Radies, Dr. Michael
Göbel und Dr. Matthias Scherr.
Ohne die Arbeit vieler Forschungspraktikanten und Bacheloranden wäre diese Arbeit
nicht möglich gewesen. Vielen Dank Harald Budde, Monika, Holzner, Dániel Izsák,
Martin Kunzmann, Andreas Maier, Gergely Rozsák, Stefanie Seel und den vielen AC3-
Praktikanten.
Vielen Dank auch an alle im Arbeitskreis, die für ein wunderbares, kreatives und
ergebnisreiches Klima gesorgt und die Zeit der Doktorarbeit zu einer schönen Zeit
gemacht haben.
Für den Rückhalt und die Liebe, die ich durch meinen besten Freund Alex und meine
Partner Jerryl und Micha in der Zeit der Doktorarbeit erfahren habe, bedanke ich mich
sehr.
Ebenso bedanke ich mich bei meinem Tanzpartner Thomas, der viele Launen ertragen
musste in dieser Zeit.
Besonders bedanken möchte ich mich bei meiner Familie und allen Freunden, die
immer da waren, wenn sie gebraucht wurden, mir zugehört und an mich geglaubt
haben.

v
Introduction

Die vorliegende Arbeit wurde in der Zeit von März 2006 bis März 2011 am Department
für Chemie der Ludwig-Maximilians-Universität München unter Anleitung
von Prof. Dr. Thomas M. Klapötke angefertigt.

vi
Introduction
1 Table of Contents
PART I INTRODUCTION ________________________________________________________ 15
1 INTRODUCTION _______________________________________________________________ 16
1.1 General _______________________________________________________________ 16
1.2 Pyrotechnics ___________________________________________________________ 17
1.3 Developments in Energetic Materials Research _______________________________ 17
1.4 Stability and Performance ________________________________________________ 19
1.5 Explosives and Environment ______________________________________________ 19
2 OBJECTIVES OF THE RESEARCH IN THIS THESIS __________________________________________ 20
3 PARTS AND CHAPTERS __________________________________________________________ 21
4 INTRODUCTION OF USED METHODS _________________________________________________ 21
4.1 Theory of explosion and explosion products __________________________________ 22
4.1.1 Physical and chemical explosion ________________________________________________ 22
4.1.2 Burning, deflagration and detonation ____________________________________________ 22
4.1.3 Deflagration to Detonation transition ___________________________________________ 23
4.1.4 Brisance vs. Explosiveness _____________________________________________________ 23
4.2 Calculation of energetic properties using EPXLO5 code[29] _______________________ 24
4.2.1 Shock wave propagation and Chapman-Jouguet velocity ____________________________ 24
4.2.2 Becker-Kistiakovsky-Wilson equation of state (BKW-EOS) ____________________________ 24
4.2.3 Explosion products - Kistiakovsky-Wilson and Springall-Roberts Rules[2a]________________ 24
4.2.4 Input parameters: Oxygen balance, heat of formation and density ____________________ 25
4.3 Practical methods_______________________________________________________ 25
4.3.1 Sensitivity testing ____________________________________________________________ 25
4.3.2 Determination of density _____________________________________________________ 27
4.3.3 Measuring the Heat of formation _______________________________________________ 28
5 REFERENCES _________________________________________________________________ 28
PART II EXPLOSIVE UREA DERIVATIVES ___________________________________________ 31
CHAPTER I A COMPREHENSIVE STUDY ON N,N´-BIS(TRIS(NITRATOMETHYL)METHYL)OXAMIDE _________ 33
1 INTRODUCTION _______________________________________________________________ 34
2 RESULTS AND DISCUSSION _______________________________________________________ 35
2.1 Comparison of crystal structures ___________________________________________ 35
2.2 Vibrational and thermodynamical data and Calculations _______________________ 39
2.2.1 Thermodynamical calculation and experimental data _______________________________ 42
2.3 Electrostatic potential (ESP) and Decomposition ______________________________ 45
2.4 Thermostability: DSC and RADEX measurements ______________________________ 47
2.5 Energetic properties _____________________________________________________ 48
2.5.1 Comparison of energetic properties of BTNMMoxamide to common explosives _________ 48
2.5.2 Koenen (steel sleeves) test ____________________________________________________ 49
3 CONCLUSIONS ________________________________________________________________ 50
4 EXPERIMENTAL _______________________________________________________________ 51
4.1 Crystal structures _______________________________________________________ 51
4.2 Properties _____________________________________________________________ 51
4.3 Spectroscopic data and elemental analysis __________________________________ 51
4.4 Preparation____________________________________________________________ 51
5 REFERENCES _________________________________________________________________ 52
CHAPTER II ENERGETIC CYANURIC ACID DERIVATIVES ______________________________________ 55
1 INTRODUCTION _______________________________________________________________ 56
1.1.1 Nitro urea compounds ________________________________________________________ 57
2 DISCUSSION _________________________________________________________________ 59
2.1 Synthesis ______________________________________________________________ 59

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Introduction

2.2 Vibrational spectroscopy _________________________________________________ 59
2.2.1 N,N',N''-Tris-(nitroxymethyl)-isocyanuric acid (3) ___________________________________ 59
2.3 Thermostability ________________________________________________________ 61
2.3.1 N,N',N''-Tris-(nitroxymethyl)-isocyanuric acid (3) ___________________________________ 61
2.4 Crystal structure _______________________________________________________ 62
2.4.1 N,N',N''-Tris-(nitroxymethyl)-isocyanuric acid (3) ___________________________________ 62
2.4.2 1,3,5-Tris(hydroxyethyl)cyanuric acid(2) __________________________________________ 65
2.4.3 1,3,5-Tris(nitratoethyl)-cyanuric acid (4) __________________________________________ 66
2.5 Calculation of thermodynamic data and surface potential ______________________ 68
2.5.1 Electrostatic surface potential of N,N',N''-Tris-(nitroxymethyl)-isocyanuric acid(3) ________ 68
2.5.2 Electrostatic surface potential of N,N',N''-Tris-(nitroxyethyl)- isocyanuric acid (4) _________ 69
2.5.3 Calculation of the enthalpy of formation __________________________________________ 69
2.1 Energetic Properties ____________________________________________________ 71
2.1.1 Detonation Parameters _______________________________________________________ 71
3 CONCLUSIONS _______________________________________________________________ 72
4 EXPERIMENTAL _______________________________________________________________ 73
4.1 Crystal structures _______________________________________________________ 73
4.2 Properties_____________________________________________________________ 73
4.3 Spectroscopic data and elemental analysis __________________________________ 73
4.4 Preparation ___________________________________________________________ 73
5 REFERENCES _________________________________________________________________ 75
CHAPTER III N2,N4,N6-TRIS(TRIS(NITRATOMETHYL)METHYL)-1,3,5-TRIAZINO-2,4,6-TRICARBOXAMIDE (NOX-
1) – BIG AND BANG _______________________________________________________________ 79
1 INTRODUCTION _______________________________________________________________ 80
2 DISCUSSION _________________________________________________________________ 81
2.1 Structure of triazine derivatives ___________________________________________ 81
2.1.1 Description of the molecule structure and the monoclinic crystal structure in comparison to
the reported hexagonal structure _______________________________________________________ 83
2.2 Synthesis _____________________________________________________________ 88
2.3 Thermodynamical and Spectroscopic Characterization _________________________ 89
2.4 Crystal structure data ___________________________________________________ 91
2.5 Energetic data _________________________________________________________ 93
3 CONCLUSIONS _______________________________________________________________ 93
4 EXPERIMENTAL PART ___________________________________________________________ 94
4.1 Instrumental setups_____________________________________________________ 94
PD-XRAY ___________________________________________________________________________ 94
IR samples _________________________________________________________________________ 94
NMR-samples _______________________________________________________________________ 94
RAMAN samples ____________________________________________________________________ 94
DSC Measurements __________________________________________________________________ 94
SC-XRAY data _______________________________________________________________________ 94
NCS-Elemental analysis _______________________________________________________________ 94
Mass Spectrometry __________________________________________________________________ 94
Friction and impact sensitivity _________________________________________________________ 94
4.2 Prepartation __________________________________________________________ 94
4.2.1 [1,3,5]Triazine-2,4,6-tricarboxylic acid triethyl ester (2) ______________________________ 94
4.2.2 N2,N4,N6-Tris(tris(hydroxymethyl)methyl)-1,3,5-triazino-2,4,6-tricarboxamide (TTHMM-TCA, 3)
95
4.2.3 N2,N4,N6-Tris(tris(nitratomethyl)methyl)-1,3,5-triazino-2,4,6-tricarboxamide (TTNMM-TCA,
NOX, 4) 95
5 REFERENCES _________________________________________________________________ 96
PART III ENERGETIC MATERIALS BASED ON 1,2,4-OXADIAZOLE DERIVATIVES ____________ 99

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Introduction
CHAPTER IV 3,3’-BIS-(1,2,4-OXADIAZOL-5-ONE) AND DERIVATIVES – A COMPREHENSIVE STUDY _______ 101
1 COMPARISON OF 3,3'-BIS-1,2,4-OXADIAZOL-5-ONE AND 5,5'-BIS-1H-TETRAZOLE ______________ 102
1.1 Introduction __________________________________________________________ 102
1.2 Discussion ____________________________________________________________ 102
1.3 Synthesis _____________________________________________________________ 106
1.4 Conclusions ___________________________________________________________ 107
1.5 Experimental _________________________________________________________ 107
1.5.1 Crystal structures ___________________________________________________________ 107
1.5.2 Properties _________________________________________________________________ 107
1.5.3 Spectroscopic Data and elemental analysis ______________________________________ 107
1.5.4 Preparation _______________________________________________________________ 107
1.6 References ___________________________________________________________ 108
2 INSENSITIVE EXPLOSIVES AND PROPELLANTS BASED 1,2,4-OXADIAZOL DERIVATIVES _______________ 110
2.1 Introduction __________________________________________________________ 110
2.2 Syntheses ____________________________________________________________ 111
2.3 Crystal structures ______________________________________________________ 112
2.3.1 Diammonium bis-(1,2,4-oxadiazol-5-onate ) _____________________________________ 112
2.3.2 Dihydrazinium bis-(1,2,4-oxadiazol-5-onate) _____________________________________ 114
2.3.3 Diguanidinium bis-(1,2,4-oxadiazol-5-onate) (G OD, 6) _____________________________ 116
2
2.3.4 Bis-aminoguanidinium 3,3‘-bis-(1,2,4-oxadiazol-5-onate) (AGOD, 7) _________________ 119
2
2.3.5 Di-triaminoguanidinium 3,3‘-bis-(1,2,4-oxadiazol-5-onate) (TAG OD, 9) _______________ 121
2
2.4 Energetic properties ____________________________________________________ 123
2.5 Conclusions ___________________________________________________________ 124
2.6 Experimental _________________________________________________________ 125
2.6.1 Crystal structures ___________________________________________________________ 125
2.6.2 Properties _________________________________________________________________ 125
2.6.3 Spectroscopic Data and elemental analysis ______________________________________ 125
2.6.4 Preparation _______________________________________________________________ 125
2.7 References ___________________________________________________________ 128
3 SMOKELESS PYROTECHNICAL COLORANTS BASED ON 3,3’-BIS-(1,2,4-OXADIAZOL-5-ONE SALTS ______ 130
3.1 Introduction __________________________________________________________ 130
3.2 Discussion ____________________________________________________________ 131
3.2.1 Syntheses _________________________________________________________________ 131
3.2.2 Crystal structures ___________________________________________________________ 132
TETRAAQUA-3,3′-BIS(1,2,4-OXADIAZOL-5-ON)-ATO COPPER(II) _______________________________ 135
3.2.3 Thermostability ____________________________________________________________ 142
3.3 Conclusion ___________________________________________________________ 144
3.4 Experimental _________________________________________________________ 144
3.4.1 Crystal structures ___________________________________________________________ 144
3.4.2 Properties _________________________________________________________________ 144
3.4.3 Spectroscopic Data and elemental analysis ______________________________________ 144
3.4.4 Preparation _______________________________________________________________ 145
3.5 References ___________________________________________________________ 146
CHAPTER V 3,5-DIAMINO-1,2,4-OXADIAZOLE – A SUBSTITUTE FOR GUANYLUREA IN ENERGETIC MATERIALS
149
1 INTRODUCTION ______________________________________________________________ 150
2 RESULTS AND DISCUSSION ______________________________________________________ 151
2.1 Synthesis and Characterization of 3,5-diamino-1,2,4-oxadiazole (DAOd, 1) ________ 151
2.1.1 3,5-diamino- 1,2,4-Oxadiazole (1, DAOd) ________________________________________ 151
2.2 Syntheses of 3,5-diamino-1,2,4(4H)-oxadiazolium salts ________________________ 159
2.2.1 The 3,5-diamino-1,2,4(4H)-oxadiazolium cation __________________________________ 159
2.2.2 3,5-Diamino-1,2,4-oxadiazolium nitrate (2) ______________________________________ 162
2.2.3 3,5-Diamino-1,2,4-oxadiazolium perchlorate (3) __________________________________ 163

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Introduction

2.2.4 3,5-Diamino-1,2,4-oxadiazolium picrate (4) ______________________________________ 169
2.2.5 3,5-Diamino-1,2,4-oxadiazolium dinitramide (5) ___________________________________ 172
2.2.6 2.3.6 3,5-Diamino-1,2,4-oxadiazolium-5-aminotetrazolate (6) _______________________ 174
2.2.7 3,5-Diamino-1,2,4-oxadiazolium-5-nitrotetrazolat (IX) ______________________________ 175
2.2.8 3,5-Diamino-1,2,4-oxadiazolium-5,5’-azotetrazolate (X) ____________________________ 176
2.2.9 3,5-Diamino-4-methyl-1,2,4-oxadiazolium iodide (XI) ______________________________ 177
2.3 Synthesis of complex bond 3,5-diamino-1,2,4-oxadiazole (7) ___________________ 177
2.4 Diazotation reaction of 1 by sodium nitrite (i) _______________________________ 178
2.5 Oxidation and Nitration of 3,5-diamino-1,2,4-oxadiazole (1) ___________________ 179
2.5.1 Oxidation or nitration with HNO (100 %) ________________________________________ 181
3
2.5.2 Oxidation or nitration with HNO (100 %) and H SO (conc.) _________________________ 181
3 2 4
2.5.3 Oxidation or nitration by sodium nitrite (ii–iv) ____________________________________ 181
2.5.4 Oxidation with H SO (conc.), HO (30 %) and (NH ) SO (v) ________________________ 182
2 4 2 2 42 2 8
2.5.5 Oxidation by potassium permanganate (vi) _______________________________________ 182
2.5.6 Oxidation by ammonium dichromate (vii) ________________________________________ 183
2.5.7 Oxidation by bromine (viii) ____________________________________________________ 183
2.5.8 Nitration with HNO (100%) and Ac O ___________________________________________ 184
3 2
2.6 Energetic Data ________________________________________________________ 184
3 SUMMARY AND CONCLUSIONS ___________________________________________________ 185
3.1 Summary ____________________________________________________________ 185
3.1.1 Energetic salts of DAOd ______________________________________________________ 186
3.1.2 Oxidation, Nitration and Diazotation of DAOd. ____________________________________ 186
3.2 Conclusion and Outlook ________________________________________________ 187
4 EXPERIMENTAL PART __________________________________________________________ 187
4.1 Common_____________________________________________________________ 187
4.2 Analytical apparatus ___________________________________________________ 187
4.3 Calculations __________________________________________________________ 189
4.4 Preparation of energetic DAOd (1) and salts thereof __________________________ 191
4.5 Oxidation and Nitration products of DAOd(1) _______________________________ 194
5 REFERENCES ________________________________________________________________ 197
CHAPTER VI 3-AMINO-1,2,4-OXADIAZOL-5-ONE – THE INSENSITIVE 5-AMINO-TETRAZOLE ? COMMONS AND
DIFFERENCES 201
1 INTRODUCTION ______________________________________________________________ 202
2 RESULTS AND DISCUSSION ______________________________________________________ 204
2.1 Synthesis of aOD ______________________________________________________ 204
2.1.1 Overview __________________________________________________________________ 205
2.1.2 Synthetic Route A ___________________________________________________________ 206
2.1.3 Synthesis route B ___________________________________________________________ 209
2.1.4 One-Pot-Synthesis according to route B _________________________________________ 219
2.1.5 Summary __________________________________________________________________ 220
2.2 Solubility of aOD ______________________________________________________ 220
2.3 Azo-coupling of aOD ___________________________________________________ 221
2.4 Salts of aOD __________________________________________________________ 222
2.4.1 Copper aOD (9) _____________________________________________________________ 222
2.4.2 Silver aOD (10) _____________________________________________________________ 223
2.4.3 Strontium aOD (11) trihemihydrate _____________________________________________ 223
2.4.4 Barium aOD (12) ____________________________________________________________ 224
2.4.5 Aminoguanidinium aOD (13) __________________________________________________ 224
2.4.6 Sodium aOD (14) monohydrate ________________________________________________ 225
2.4.7 Summary __________________________________________________________________ 229
2.5 Methylation of 3-amino-1,2,4(4H)-oxadiazol-5-one __________________________ 230
2.6 Synthesis of salts with aODH+ as cation ____________________________________ 231
2.6.1 Summary __________________________________________________________________ 241

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