Two Novel Melt-Cast Cocrystal Explosives Based on 2,4-Dinitroanisole with Significantly Decreased Melting Point

Abstract

Typically, explosive formulations are processed in large anchor melt-cast kettles heated by hot water or steam under low shear conditions. Hence, it is difficult to use some melt-cast carrier explosives with high melting points (close to or even higher than the steam temperature), such as 2,4-dinitroanisole (DNAN), 1,3,3-trinitroazetidine (TNAZ), and 3,4-bis­(3-nitrofurazan-4-yl)­furoxan (DNTF), for realizing applications with the continued operation of existing melt-cast facilities and without major plant modifications. To address this need, two novel melt-cast-able energetic cocrystals based on DNAN, namely, (1) DNAN/NA (2-nitroaniline) 1:1 and (2) DNAN/DNB (1,3-dinitrobenzene) 1:1, were obtained. The melting point of cocrystals 1 (67.5 °C) and 2 (48.0 °C) was distinctly lower than that of their coformers, namely, DNAN (95.0 °C), NA (71.5 °C), and DNB (89.5 °C). Moreover, they also exhibited better safety and thermostability compared with traditional melt-cast carrier explosives such as DNAN and trinitrotoluene (TNT). Thus, these novel DNAN cocrystals can provide new insights into the future design and modification of novel melt-cast carrier explosives.

Host–guest energetic materials: a promising strategy of incorporating small insensitive molecule into the lattice cavities of 2,4,6,8,10,12-hexanitrohexaazaisowurtzitane to enhance the safety on the premise of maintaining the excellent energy density

“…In addition, the weak hydrogen bond of O(13)–H(13)⋯O(2) (2.81 Å, 132°) between the O atom of HNIW and the H atom on the O–H group of MA combined with the HNIW and MA. The percentage of O⋯H interactions in HNIW-MA was greater than that in ε-HNIW and HNIW-CO 2 by analyzing through the Hirshfeld surface method 22 (Fig. 3d–g and Table S3†).…”

Review of the Intermolecular Interactions in Energetic Molecular Cocrystals

“…Similarly, DNBT, DNAN, and related coformers (Figure 1j,q) possess π-conjugated structures. 67,68 Both DNPP and 3,4-DNP (Figure 1j3,j4) contain pyrazole rings; NA and DNB both possess a benzene ring each, facilitating to the face to face π stacking in cocrystals. In addition, these molecules are both HBAs and HBDs.…”

Exploring the thermal decomposition and detonation mechanisms of 2,4-dinitroanisole by TG-FTIR-MS and molecular simulations

“…[1][2][3][4][5][6][7][8][9][10][11] Among them, 2,4-dinitroanisole (DNAN) is an insensitive melt-cast matrix ingredient, which was used to prepare Amatol-40 explosives in WWII. 11,12 Since the 1980s, DNAN has again aroused strong attention and has become a promising energetic material to replace the traditional trinitrotoluene (TNT) in melt-cast explosives to make them less sensitive [13][14][15][16][17][18][19] owing to its kinetic inertness and thermal stability. Various DNAN-based melt-pour explosive formulations have been developed [20][21][22][23][24][25][26][27][28][29][30][31][32] and put into service.…”

“…It is unsurprising that the use of DNAN to desensitize novel emerging sensitive high-energy density explosives has become very promising. 27,[45][46][47][48][49][50][51] On the other hand, the Evans-Polanyi-Semenov (E-P-S) equation [52][53][54][55][56] describes a relationship between activation energies (E) of many radical reactions and their heats of reaction ðDHÞ: E ¼ B þ a 0 * DH, where B is a constant and can be viewed as a measure of how far a reaction has proceeded along the reaction coordinate when the transition state (TS) is reached. Based on the EPS equation, it was found that for polynitroaromatics, such as TNT and TATB, the activation energy for thermal decomposition is inversely proportional to the heat of detonation.…”