hexanitrohexaazaisowurzitane and octogen

2,4,6,8,10,12-Hexanitro-2,4,6,8,10,12-hexaaza-isowurtzitane (HNIW), also known as CL-20 and octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX), are highly energetic materials which have been popular in national defense industries for years. This study established the models of thermal decomposition and thermal explosion hazard for HNIW and HMX. Differential scanning calorimetry (DSC) data were used for parameters determination of the thermokinetic models, and then these models were employed for simulation of thermal explosion in a 437L barrel reactor and a 24 kg cubic box package. Experimental results indicating the best storage conditions to avoid any violent runaway reaction of HNIW and HMX were also discovered. This study also developed an efficient procedure regarding creation of thermokinetics and assessment of thermal hazards of HNIW and HMX that could be applied to ensure safe storage conditions.

Topics: Azocines; Bridged-Ring Compounds; Calorimetry, Differential Scanning; Explosions; Explosive Agents; Models, Theoretical; Nitro Compounds; Thermodynamics

Hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX, I) and octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) hydrolyze at pH > 10 to form end products including NO2-, HCHO, HCOOH, NH3, and N2O, but little information is available on intermediates, apart from the tentatively identified pentahydro-3,5-dinitro-1,3,5-triazacyclohex-1-ene (II). Despite suggestions that RDX and HMX contaminated groundwater could be economically treated via alkaline hydrolysis, the optimization of such a process requires more detailed knowledge of intermediates and degradation pathways. In this study, we hydrolyzed the monocyclic nitramines RDX, MNX (hexahydro-1-nitroso-3,5-dinitro-1,3,5-triazine), and HMX in aqueous solution (pH 10-12.3) and found that nitramine removal was accompanied by formation of 1 molar equiv of nitrite and the accumulation of the key ring cleavage product 4-nitro-2,4-diazabutanal (4-NDAB, O2NNHCH2NHCHO). Most of the remaining C and N content of RDX, MNX, and HMX was found in HCHO, N2O, HCOOH, and NH3. Consequently, we selected RDX as a model compound and hydrolyzed it in aqueous acetonitrile solutions (pH 12.3) in the presence and absence of hydroxypropyl-beta-cyclodextrin (HP-beta-CD) to explore other early intermediates in more detail. We observed a transient LC-MS peak with a [M-H] at 192 Da that was tentatively identified as 4,6-dinitro-2,4,6-triaza-hexanal (O2NNHCH2NNO2CH2NHCHO, III) considered as the hydrolyzed product of II. In addition, we detected another novel intermediate with a [M-H] at 148 Da that was tentatively identified as a hydrolyzed product of III, namely, 5-hydroxy-4-nitro-2,4-diaza-pentanal (HOCH2NNO2CH2NHCHO, IV). Both III and IV can act as precursors to 4-NDAB. In the case of the polycyclic nitramine 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (CL-20), denitration (two NO2-) also led to the formation of HCOOH, NH3, and N2O, but neither HCHO nor 4-NDAB were detected. The results provide strong evidence that initial denitration of cyclic nitramines in water is sufficient to cause ring cleavage followed by spontaneous decomposition to form the final products.

Topics: Azocines; Bridged-Ring Compounds; Environmental Pollutants; Heterocyclic Compounds, 1-Ring; Hydrogen-Ion Concentration; Hydrolysis; Nitro Compounds; Triazines