THE PREPARATORY MANUAL OF EXPLOSIVES

A LABORATORY MANUAL

Jared B. Ledgard, A.A.S., B.S., M.A.

Organic chemist, Inventor Seattle, Washington USA

i

ii

Contents Section I: Introduction page 1 Chapter 1 page 1

Chemical bonding: oxidation states page 1 Ionic compounds and ionic bonds page 2 Covalent compounds and covalent bonds page 3 Understanding chemical structures and formulas page 4 Chemical reactions page 6 Language of chemistry page 6 Conversion factors page 7

Section II: Tutorial page 9 Chapter 2 page 9

Lab safety page 9 Laboratory equipment page 10 Methods of heating page 11 Methods of cooling page 13 Extraction page 15 Recrystallization, product recovery, and filtration page 17 Washing liquid and solids page 20 Drying agents, and drying liquids page 21 Distillation page 22 Final lesson: A tutorial on explosives page 24 The dynamics of detonation page 25 Detonation verses deflagration and combustion page 26 Primary, and secondary explosives page 27 Initiation of explosives page 28 The power of explosives page 29 The physical effects of explosives page 30

Section III: Chemical reagents, intermediates, and solvents page 32 Chapter 3 page 32 Section IV: Explosives and explosive compositions page 65 Chapter 4: The preparation of metal azide, fulminates, and nitrides page 66

4-01. AZ AZ Ammonium azide page 66 4-02. CZ Cupric azide page 67 CZ rim fire composition page 68 4-03. SZ Silver azide page 68 4-04. MZ Mercury azide page 69 4-05. LZ Lead azide page 70 4-06. Mercury fulminate page 71 Priming mixture page 72 Gunpowder page 72 Rim fire composition page 72 Rim fire composition page 72 Initiating mixture page 73 4-07. Silver fulminate page 73 Priming mixture page 74 4-08. Copper fulminate page 74 4-09. Silver nitride page 75 4-10. Mercury nitride page 75 4-11. Sulfur nitride page 77

Chapter 5: Preparation of Azides and azo nitros page 80 5-01. BDPF Bis(1,3-diazido-2-propyl)formal page 80

CONTENTS

iii

5-02. TETRAZIDE Isocyanogen tetraazide page 82 5-03. TAEN Triazoethanol nitrate page 83 TAEN dynamite composition page 84 5-04. AZIDOETHYL Tris(2-azidoethyl)amine page 84 5-05. DANP 1,3-Diazido-2-nitrazapropane page 86 DANP explosive composition page 88 5-06. DIANP 1,5-diazido-3-nitraza pentane page 89 DIANP propellant page 90 5-07. Diazodinitrophenol 4,6,-Dinitro-2-diazophenol page 91 5-08. HNTCAB Hexanitrotetrachloroazobenzene; 2,4,6,2',4',6'-Hexanitro-3,5,3',5'- tetrachloroazobenzene page 94 5-09. DNAT 1,1'-dinitro-3,3'-azo-1,2,4-triazole page 96 5-10. ADNB 4-Azido-4,4-dintro-1-butyl acetate page 98 5-11. ADBN. 4-Azido-4,4-dintro-1-butyl nitrate page 100

Chapter 6: The preparation of aza/oxa nitramines page 103 6-01. TNTC. 2,4,6-trinitro-2,4,6-triazacyclohexanone page 103 Azadine explosive composition page 105 TNTC plastic explosive page 105

6-02. DDD. 5,7-dinitro-5,7-diaza-1,3-dioxabicyclo[3:3:0] octan-2-one page 105 DDD composition page 107 6-03. TEX. 4,10-dinitro-2,6,8-12-tetraoxa-4,10-diazatetracyclo- [5.5.0.05,903,11]-dodecane page 107 6-04. DNFA-P. 1,4-dinitrofurazano[3,4-b]piperazine page 110

Chapter 7: The preparation of cyclic nitramines page 113 7-01. RDX. Cyclonite; Hexahydro-1,3,5-trinitro-1,3,5-triazine; 1,3,5-trinitrohexahydro-s-triazine; cyclotrimethylenetrinitramine page 113 Composition B page 118 RDX explosive composition page 119 PBX explosive composition page 119 RDX high performance rocket propellant page 119 C3 plastic explosive page 120 C4 plastic explosive page 120 RDX explosive munitions page 121 7-02. Solex. 1-(N)-acetyl-3,5,7-trinitro-cyclotetramethylene Tetramine page 123 Solex explosive composition page 124 7-03. HMX. Octogen; 1,3,5,7-tetranitro-1,3,5,7- tetraazacyclooctane; alpha-HMX and beta-HMX page 124 HMX gun propellant page 128 HMX explosive page 128 HMX plastic explosive page 128 PBX B HMX explosive composition page 129 HMX explosive page 129 7-04. NINHT. 2-nitroimino-5-nitro-hexahydro-1,3,5-triazine page 129 7-05. TNAD. 1,4,5,8-Tetranitro-1,4,5,8-tetraazadecalin page 131 7-06. DPT. 1,5-methylene-3,7-dinitro-1,3,5,7- tetraazacyclooctane page 134

Chapter 8: The preparation of nitramines page 136 8-01. DITN. Diisopropylamine trinitrate page 136 8-02. DMMD. 2,4-dinitro-2,4-diazapentane page 137 8-03. Tetryl. Nitramine; N-methyl-N,2,4,6- tetranitrobenzenamine page 139 Tetry explosive booster compostion page 141 8-04. MNA. Methylnitramine page 141 8-05. Methylene dinitramine page 144 8-06. HNIW. 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-

CONTENTS

iv

Hexaazaisowurtzitane page 146 Chapter 9: The preparation of nitramines page 151

9-01. ADN. Ammonium dinitramide page 151 9-02. KDN. Potassium dinitramide page 154

Chapter 10: The preparation of amino nitro benzenes page 158 10-01.Tetraniline. Tetranitro aniline page 158 Tetraniline explosive page 160 10-02. TATB. 1,3,5-triamino-2,4,6-trinitrobenzene page 160 RDX/TATB booster composition page 164

TAT TATB/TNT explosive composition page 164 10-03. DATB. 1,3-diamino-2,4,6-trinitrobenzene page 165 10-04. DATBA. 5-Carboxy-1,3-diamino-2,4,6- trinitrobenzene page 167 10-05. A-NPNT. 4-amino-N,2,3,5,6-pentanitrotoluene page 169 10-06. UDTNB. 5-ureido-1,3-diamino-2,4,6-trinitrobenzene page 171 10-07. DNPU. 2,4-dinitrophenylurea page 174 10-08. ADNBF. 7-amino-4,6-dinitrobenzofuroxan page 176 10-09. TNPU. N,N'-bis(2,4,6-trinitrophenyl)urea page 177

Chapter 11: The preparation of nitro benzenes page 180 11-01. TNT. 2,4,6-trinitrotoluene; trinitrotoluene page 180 Composition A1 page 185 TNT blasting composition page 186 TNT wax composition page 186 Hexotonal RDX/TNT explosive composition page 187 Octol explosive composition page 187 TNT explosive munitions page 187 11-02. F-TNB. 1,3,5-trifluoro-2,4,6-trinitrobenzene page 188 11-03. TCTNB. Trichlorotrinitrobenzene; 1,3,5-trichloro-2,4,6- Trinitrobenzene page 190 11-04. Picryl Chloride. 1-chloro-2,4,6-trinitrobenzene page 191 11-05. TNBCl. Trinitrobenzylchloride page 192

Chapter 12: The preparation of poly nitro benzenes page 194 12-01. HNB. Hexanitrobibenzyl; 2,2', 4,4', 6,6'- hexanitrobibenzyl page 194 12-02. HNS. Hexanitrostilbene page 195 12-03. TNTPB. 1,3,5-trinitro-2,4,6-tripicrylbenzene page 198 12-04. PNT. 2,3,4,5,6-pentanitrotoluene page 200 12-05. HNBP. Hexanitrobiphenyl page 202 12-06. Hexaditon. 2,2',4,4',6,6'-hexanitrodiphenylmethane page 203 12-07. TNN. Nitronaphthalene; 1,3,6,8-tetranitronaphthalene page 205

Chapter 13: The preparation of nitrate esters page 209 13-01. EDT. N,N'-di-(2-ethanol)ethylenediamine tetranitrate page 209 13-02. Nitrocellulose. Nitrated cellulose; Gun cotton page 212 Gun propellant page 219 Gun propellant page 219 Smokeless powder page 219 Blasting powder page 220 Blasting powder page 220 13-03. ETN. Erythritol tetranitrate page 220 13-04. PEN. Pentaerythritol trinitrate page 221 13-05. PETN. Pentaerythritol tetranitrate; 2,2-Bis[(nitrooxy)- methyl]-1,3-propanediol dinitrate page 225 Blasting explosive page 229 PETN bonded explosive page 229 PETN propellant charge page 229 Pentolite PETN composition page 229 Semtex PETN explosive page 229 PETN explosive munitions page 230 13-06. NQ. Nitroglycerine page 230

CONTENTS

v

HESP high-energy smokeless powder page 232 Dynamite page 233 13-07. Nitro starch. Nitrated cornstarch page 233 Nitro starch explosive composition page 234 13-08. EGDN. Ethylene glycol dinitrate page 234 13-09. Metriol. page 235 13-10. Nitropropylene. PGDN. Propylene glycol dinitrate page 237

Chapter 14: The preparation of polyhydric nitrate esters page 240 14-01. Hexanitrate. Sorbitol hexanitrate page 240 14-02. Quebrachitol nitrate. Monomethyl cyclohexanepentanitrate page 241 14-03. Inositol nitrate. Inositol hexanitrate page 243 14-04. MGP. N-Methyl gluconamide pentanitrate page 245 14-05. MON. Maltose octanitrate page 246 14-06. MX. Nitromannite; page 248 14-07. PVN. Polyvinylnitrate page 250

Chapter 15: The preparation of nitrate ester nitramines page 253 15-01. NMHAN. N-Nitro-N-methylhydroxy acetamidenitrate page 253 15-02. DINA. Dinitroxydiethylnitramine page 254 15-03. DNAN. Dinitroxydiethylamine nitrate page 259 15-04. NENA. N-(2-Nitroxyethyl)nitramine page 261 15-05. Silver NENA. N-(2-Nitroxyethyl) nitramine, silver salt page 263

Chapter 16: The preparation of nitro triazoles page 265 16-01. NTA. 3,5-Dintro-1,2,4-triazole page 265 16-02. MNTA. 1-Methyl-3,5-dinitro-1,2,4-triazole page 267 16-03. CDNTA. 3,5-Dinitro-1,2,4-triazole-copper salt page 269 16-04. NTO. 3-nitro-1,2,4-triazol-5-one page 271 16-05. 5-NDTT. 5-nitro-2(3,5-diamino-2,4,6-trinitrophenyl)- 1,2,4-triazole page 272

Chapter 17: The preparation of nitro tetrazoles page 276 17-01. SATP. di-Silver aminotetrazole perchlorate page 276 17-02. CNTA. Copper salt of 5-nitrotetrazole page 277 CNTA priming mixture page 280 17-03. HGNTA. Mercury nitrotetrazole page 280 HGNTA priming mixture page 282 17-04. LNTA. Lead nitrotetrazole, basic salt page 282 17-05. TADA. 5,5'-bi-1H-tetrazole diammonium salt page 284

Chapter 18: The preparation of nitro phenyls page 287 18-01. TPG. 2,4,6-trinitrophloroglucinol page 287 18-02. DNP. 2,4-Dinitrophenol page 288 Phenolene explosive composition page 290 18-03. DNR. 4,6-dinitroresorcinol page 290 18-04. Picric Acid. 2,4,6-trinitrophenol page 291 Pentotal explosive composition page 294 18-05. Styphnic Acid. 2,4,6-trinitro-1,3-benzenediol page 294 18-06. Picramic acid. 2-amino-4,6-dinitrophenol page 296 18-07. Methylpicric acid. 2,4,6-trinitro-3-methylphenol page 298 Explosive composition page 299 18-08. TA. Trinitroanisole page 300

Chapter 19: The preparation of nitro phenyl salts page 302 19-01. Lead-TNP. Trinitrophloroglucinol lead salt page 302 Lead-TNP ignition/initiating mixture page 303 19-02. Barium Styphnate page 304 19-03. Lead Styphnate. 2,4,6-trinitro-lead-II-resorcinate page 305 19-04. Ammonium Picramate. Ammonium 2-amino-4,6- dinitrophenolate; Ammonium-2-amino-4,6-dinitropicrate page 308 19-05. AP. Ammonium Picrate page 310 19-06. Lead Picrate. 2,4,6-Trinitro-lead-phenolate basic page 311

CONTENTS

vi

Lead pircrate initiating mixture page 312 19-07. Sodium picramate. Ammonium 2-amino-4,6- dinitrophenolate; Ammonium-2-amino-4,6-dinitropicrate page 313 Chapter 20: The preparation of nitrates, chlorates, and perchlorates page 315 20-01. AN. Ammonium Nitrate page 315 AN/Aluminum blasting prill page 317 Blasting composition page 317 ANFO page 317 ANFO B page 317 AN black powder page 318 AN explosive munitions page 318 20-02. AC. Ammonium chlorate page 319 20-03. APC. Ammonium perchlorate page 320 Perchlorate high performance rocket propellant page 321 Perchlorate high performance rocket propellant page 321 Perchlorate high performance rocket propellant page 322 20-04. PCB. Perchlorylbenzene page 322 20-05. Nitro-PCB. 3-Nitroperchlorylbenzene page 323 20-06. BDC. Biguanide diperchlorate page 325 20-07. EDDN. Ethylenediamine dinitrate page 326

Chapter 21: The prepartion of paraffins and their derivatives page 328 21-01. Nitroform. Trinitromethane page 328 21-02. HNF. Hydrazine nitroform; Hydrazinium nitroformate page 332 21-03. KNF. Potassium nitroform page 334 21-04. Silver nitroform page 335 21-05. TNM. Tetranitromethane page 336 21-06. TBA. 4,4,4-Trinitrobutyraldehyde page 340 21-07. TNB. 4,4,4-Trinitro-1-butanol page 341 21-08. 4,4-DNB. 4,4-Dintro-1-butanol page 343 21-09. HNH-3. 1,1,1,6,6,6-Hexanitrohexyne-3 page 344 21-10. TNP. 1,1,1,2-Tetranitropropane page 346 21-11. TNEN. 2,2,2-Trinitroethyl-2-nitroxyethyl ether page 347 21-12. NTND. 2-Methyl-2-(N-nitro-N-trinitroethylamino)-1,3- propyl dinitrate page 352

Chapter 22: Miscellaneous page 355 22-01. TNA. 1,3,5,7-Tetranitroadamantane page 355 22-02. TND. 1,4,6,9-Tetranitrodimantane page 358 22-03. Nitroguanidine page 361 22-04. NU. Nitrourea page 362 22-05. Acetone-P; Acetone peroxide page 363 22-06. Tetracene. Tetrazene page 265

References page 367