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High energy density materials based on tetrazole and nitramine compounds [Elektronische Ressource] : synthesis, scale-up and testing / Jan J. Weigand

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DISSERTATION ZUR ERLANGUNG DES DOKTORGRADES DER FAKULTÄT FÜR CHEMIE UND PHARMAZIE DER LUDWIG-MAXIMILIANS-UNIVERSITÄT MÜNCHEN HIGH ENERGY DENSITY MATERIALS BASED ON TETRAZOLE AND NITRAMINE COMPOUNDS – SYNTHESIS, SCALE-UP AND TESTING VORGELEGT VON JAN J. WEIGAND AUS REISBACH 2005 Erklärung Diese Dissertation wurde im Sinne von § 13 Abs. 3 bzw. 4 der Promotionsordnung vom 29. Januar 1998 von Prof. Dr. Thomas M. Klapötke betreut. Ehrenwörtliche Versicherung Diese Dissertation wurde selbständig, ohne unerlaubte Hilfsmittel erarbeitet. München, den 27. März 2005 ……………………………………… (Jan J. Weigand) Dissertation eingereicht am: 27.04.2005 1. Gutachter Prof. Dr. Thomas M. Klapötke 2. Gutacher PD Dr. Axel Schulz Mündliche Prüfung am 25.05.2005 Mom, I love you! THOMAS, NIELS, ROSEMARIE, DOMINIK, RENATE, PETER, HARTMUT AND ZACHARY Thank you! Acknowledgement I would like to thank Prof. Dr. Thomas M. Klapötke for all his guidance and encouragement during this study and for his invaluable mentorship. I would like to thank the group of Prof.

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Published 01 January 2005
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DISSERTATION ZUR ERLANGUNG DES DOKTORGRADES
DER FAKULTÄT FÜR CHEMIE UND PHARMAZIE
DER LUDWIG-MAXIMILIANS-UNIVERSITÄT MÜNCHEN



HIGH ENERGY DENSITY MATERIALS
BASED ON TETRAZOLE AND NITRAMINE
COMPOUNDS

SYNTHESIS, SCALE-UP AND TESTING







VORGELEGT VON

JAN J. WEIGAND

AUS

REISBACH

2005
Erklärung


Diese Dissertation wurde im Sinne von § 13 Abs. 3 bzw. 4 der Promotionsordnung vom 29.
Januar 1998 von Prof. Dr. Thomas M. Klapötke betreut.




Ehrenwörtliche Versicherung

Diese Dissertation wurde selbständig, ohne unerlaubte Hilfsmittel erarbeitet.



München, den 27. März 2005








………………………………………

(Jan J. Weigand)















Dissertation eingereicht am: 27.04.2005

1. Gutachter Prof. Dr. Thomas M. Klapötke

2. Gutacher PD Dr. Axel Schulz

Mündliche Prüfung am 25.05.2005





































Mom, I love you!











































THOMAS, NIELS, ROSEMARIE,
DOMINIK, RENATE, PETER,
HARTMUT AND ZACHARY

Thank you!

Acknowledgement




I would like to thank Prof. Dr. Thomas M. Klapötke for all his guidance and encouragement
during this study and for his invaluable mentorship.


I would like to thank the group of Prof. Klapötke and the members of the Department of
Chemistry and Biochemistry for support.




JJW thanks for a FCI scholarship, DO 171/46
















Axel, Thank you! TABLE OF CONTENTS





Page
TABLE OF CONTENTS…..…...……………………………………………………… i
LIST OF TABLES………………………………………………………………...…… viii
LIST OF FIGURES…………………………………………………………………….. xi
LIST OF SCHEMES…………………………………………………………………… xvi


CHAPTER
I INTRODUCTION
1. Classification of explosives …………………………………………….. 1
1.1 High Explosives…………………………………………………. 5
1.2 Propellants………………………………………………………. 6
1.3 Pyrotechnics……………………………………………………... 7
2. Drawbacks of Explosives……………………………………………….. 7
2.1 Pyrotechnic Compositions………………………………………. 7
2.2 Gas Generators…………………………………………………...8
2.3 Liquid Propellants……………………………………………….. 9
2.4 Primary Explosives………………………………………………9
2.5 Tetrazene as Sensitizer…………………………………………...10
3. High Energy Density Materials − A Solution ?…………………….…… 10
3.1 Relationship between Guanidines and Tetrazoles……………….. 12
3.2 Goals of this Study………………………………………………. 14
3.3 Experimental Techniques………………………………………... 20
3.3.1 Thermal Analysis………………………………………...20
TGA…………………………………………………….. 20
DSC…………………………………………………….. 21
iCHAPTER Page

Bomb Calorimetry……………………………………… 24
Explosion experiments………………………………….. 24
3.3.2 Sensitivity Tests………………………………………….25
ImpactSensitivity……………………………………….26
Friction Tester…………………………………………... 27
Koenen Test…………………………………………….. 28
4. References………………………………………………………………. 30

II 5-AMINOTETRAZOLE AND AZOTETRAZOLATES
1. Introduction……………………………………………………………... 34
1.1 Tetrazoles………………………………………………………... 34
1.1.1 Tautomerism…………………………………………….. 35
1.1.2 Stability…………………………………………………. 36
1.1.3 Acid/base properties……………………………...……... 37
1.1.4 5-Aminotetrazole monohydrate (5-AT, 13) …………….. 38
1.2 Azotetrazolates…………………………………………………... 39
2. Azidoformamidinium and Guanidinium 5,5’-Azotetrazolate Salts……... 41
2.1 Synthesis of AFZT, GZT, AGZTH, DAGZT and TAGZT…… 41
2.2 Result and Discussion………………………………………….... 43
2.2.1 Raman, IR and NMR Spectroscopy …………..………… 43
2.2.2 Crystal structure of AFZT and AGZTH………………... 45
2.2.3 Thermodynamic aspects………………………………… 48
Heats of formation……………………………………… 48
Detonation pressure (P) and velocities (D)……………... 49
Impact and friction sensitivities………………………… 50
2.2.4 Thermal behavior………………………………………...50
DSC…………………………………………………….. 51
Explosion products……………………………………... 52
2.3 Conclusion………………………………………………………. 55
2.4 Experimental…………………………………………………….. 56


iiCHAPTER Page

3. Hydrazinium 5,5’-Azotetrazolate Salts………………………………...... 61
3.1 Synthesis of HZT (26), HZTH (27), and DAD (28)…….……… 62
3.2 Patent……………….………………………………………….... 63
3.3 High Temperature and Pressure FTIR study of DAD (28)……… 78
3.3.1 Experimental Method……………..…………..………… 78
3.3.2 Experimental Results ………...………...………...……... 80
3.3.3 Discussion…………….………………………………… 88
3.3.4 Conclusion………………………………………………. 90
4. STANAG 4147 and 4582…….…………………………………………. 91
4.1 Compatibility tests of HZT and HZTH with TLPs….…….....… 92
4.2 Compatibility tests of TAGZT with TLPs………...…..……...… 95
4.3 Conclusion………………………………………………………. 97
5. References………………………………………………………………. 99

III N,N-BIS-(1(2)H-TETRAZOL-5-YL)-AMINE HYDRATE (BTA)
1. Introduction……………………………………………………………... 102
1.1 Pyrotechnic composition and primers …………………………... 102
1.2 Synthesis of H bta (30)…...………...…………………………... 104 2
2- 2. The Dianion of 5-Cyanoiminotetrazoline: C N (CIT, 33).……...…..... 105 2 6
2.1 Introduction……...………………………………………….…… 105
2.2 Results and Discussion…………………………………………... 107
2.2.1 Synthesis and properties of CIT salts ………...………… 107
2.2.2 DSC of Cs CIT (34)……………………...……………... 108 2
2.2.3 In Situ X-ray Powder Diffraction of Cs CIT (34) ….…… 109 2
i 2.2.4 X-ray Structure of ( PrNH ) CIT•MeOH (35) and 34…... 110 3 2
2.2.5 Structure and bonding of the CIT dianion………………. 113
2.2.6 Crystal Structure of [Pd(C N )(NH ) ]·H O (36)……….. 115 2 6 3 3 2
2.2.7 The reaction of Cs CIT with SO ……………………….. 118 2 2
2.2.8 Crystal Structure of Cs CIT-SO •SO (37)……………… 119 2 3 2
2.2.9 CIT versus CITSO …………………...………………... 121 3
2.3 Conclusion............................…………………………………….. 122
2.4 Experimental……………………...……………………………... 123
iiiCHAPTER Page

3. H bta as HNC ligand system.……………………………………...…..... 127 2
3.1 Alkali and alkaline earth metal salts……………………………... 127
3.1.1 Raman spectroscopy…………………………………….. 128
3.1.2 Crystal structure of Li bta*5H O (40)…………....…...... 130 2 2
3.1.3 Crystal structure of Na (bta)*2H O (42)……...………… 132 2 2
3.1.4 Crystal structure of CsHbta*H O (39), Rb bta*H O (43) 2 2 2
and Csbta*H O (44)……………………………………. 134 2
3.1.5 Crystal structure of Cabta*5H O (45) and 2Babta*5H O (46)……………………………………136 2
3.1.6 Experimental…………………...………………………... 138
3.2 H bta / (NH ) [Cu(NH ) ] System………...…………………...... 143 2 4 2 3 6
3.2.1 Introduction……….…………………………………….. 143
3.2.2 Synthesis of Cu(bta)(NH ) (47), Cu(bta)(NH ) *H O (48) 3 2 3 2 2(NH ) Cu(bta) *2.5H O (49)………………………. 143 4 2 2 2
3.2.3 Crystal structure of 47 and 48…………………………… 144
3.2.4 Magnetic properties of 47, 48 and 49……………...….… 150
3.2.5 Thermal decomposition and thermodynamic aspects…… 152
3.2.6 Conclusion………………………………………………. 154
3.2.7 Experimental……………………………………………. 155
- - 3.3 H bta / CuX (X = Cl , ClO ) System………..………….........… 158 2 2 4
3.3.1 Introduction……….…………………………………….. 158
3.3.2 Synthesis…………………………………………………158
3.3.3 Molecular structure of
[CuCl (H bta)(H O)]*2H O (50)...................................... 159 2 2 2 2
3.3.4 Molecular structure of [CuCl(H bta) ]Cl (51)……........... 160 2 2
3.3.5 Molecue of [CuCl (H bta) ]*2H O (52)…….. 162 2 2 2 2
3.3.6 Molecular structure of [Cu(H bta) ](ClO ) *H O (53)…. 162 2 2 4 2 2
3.3.7 Discussion........................................................................... 163
3.3.8 Experimental…………………...………………………... 166
3.4 Conclusion…............................................……..………….........… 167
4. References……..…………...……………………………………...…..... 168

ivCHAPTER Page

IV 1,5-DIAMINO-1H-TETRAZOLE (DAT)
1. Introduction……………………………………………………………... 173
1.1 DAT ……………………………………...……………………... 173
1.2 Energetic salts…..………………………………..……………… 174
1.3 Crystal building units…...………………………..……………… 175
+ + 2. HDAT / MeDAT salts………………………………………………… 177
2.1 Synthesis………………………………………………………… 178
2.2 IR spectroscopy……….……..……………...…………………… 179
15 1 15 2.3 N Chemical Shifts and H- N Coupling Constants…………… 182
1 13 2.4 H and C NMR spectra………………………………………… 184
2.5 Molecular structure of HDATNO (59a), HDATClO (59b), 3 4
MeDATNO (61b) and MeDATN (61d)……………………... 186 3 3
2.6 Crystal structure of 59a, 61b, 59b and 61d……………………… 189
2.7 MeDATN(NO ) (61c)………………………………………...…194 2 2
2.7.1 Crystal structure of 61c………………………………..… 195
2.7.2 Closed-shell interaction in 61c………………….………. 197
2.8 Thermodynamic aspects…..…………………………………...…199
2.8.1 Heats of formation and detonation…...……………..…… 199
2.8.2 Detonation pressures and velocities………..……….…… 202
2.8.3 Sensitivity test…………………………………………... 202
2.8.4 Koenen test of 59c………………………………….…… 203
2.9 Thermal behavior ……..…….………………………………...… 204
2.9.1 DSC and TGA…………………….....……………..…… 205
2.9.2 Activation energy………...……….....……………..…… 208
2.9.3 Decomposition experiments.…….......……………..…… 208
Possible decomposition scheme for 61d………..…...….. 208
or 61b…….....……….. 212
or 61c……..………….. 215
2.10 Conclusion……....….…..…….……………………………...… 217
2.11 Experimental….....….…..…….……………………………...… 218
3. References…..……………...……………………………………...…..... 224

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