Thermal chemistry and decomposition behaviors of energetic materials with trimerizing furoxan skeleton

Abstract

Trimerizing furoxans are ideal molecular skeletons for the construction of high energetic substances due to their compact structures and high enthalpy of formations. To explore and compare the thermal behaviors of energetic materials with tandem trimerizing furoxan molecular skeleton, we reported the first systematic research on the thermochemical behaviors and decomposition mechanism of 3,4‐bis(3‐fluorodinitromethylfuroxan‐4‐yl)furoxan (BFTF), 3,4‐bis(3‐cyanofurazan)furazan oxide (BCTFO) and benzotrifuroxan (BTF). According to the research results of the DSC‐TG experiments, both the substituted furoxan based energetic compounds (BCTFO and BFTF) exhibited low melting points and complicated thermal decomposition behaviors around 240 °C, while the melting point of unsubstituted furoxan (BTF) was much higher. Their detailed decomposition mechanisms were proposed based on the experimental results through tandem techniques including in‐situ FTIR spectroscopy method and DSC‐TG‐FTIR‐MS quadruple technology, which indicated that the cleavage of substituent would trigger the decompositions of BFTF and the decomposition of trimerizing furoxan skeletons almost synchronous occurrence with substituents in BCTFO. The self‐oxidation‐reduction of the linear and annular trimerizing furoxans lead to similar decomposition fragmented small molecule products.

Convenient Preparation, Thermal Properties and X-ray Structure Determination of 2,3-Dihydro-5,6,7,8-tetranitro-1,4-benzodioxine (TNBD): A Promising High-Energy-Density Material

“…Although mixed O,N-heterocycles, such as 1,2,5-, 1,2,4-and 1,3,4-oxadiazoles [16][17][18][19][20], as well as oxadiazole N-oxides (furoxans) [21][22][23][24][25][26], are now amongst the most popular newly designed energetic compounds [27], derivatives of "pure" O-heterocycles as energetic materials have hardly been mentioned in the scientific literature (except for unstable cyclic peroxides) [28]. 1,4-Benzodioxane (also known as 1,2-ethylenedioxybenzene, benzo-1,4dioxane (old chemical names) or 2,3-dihydro-1,4-benzodioxin (new systematic name)) is one of many benzene-annulated oxygen O-heterocycles [29].…”

Convenient Preparation, Thermal Properties and X-Ray Structure Determination of 2,3-Dihydro-5,6,7,8-tetranitro-1,4-benzodioxine (TNBD): a Promising High Energy Density Material (HEDM)

“…Althought mixed O,N-heterocycles, such as 1,2,5-, 1,2,4-and 1,3,4-oxadiazoles [16][17][18][19][20], as well as oxadiazole N-oxides (furoxans) [21][22][23][24][25][26] , are now amongst the most popular newly designed energetic compounds [27], derivatives of "pure" O-heterocycles as energetic materials have hardly been mentioned in scientific literature (except for unstable cyclic peroxides) [28]. 1,4-Benzodioxane (also known as 1,2-ethylenedioxybenzene, benzo-1,4-dioxane (old chemical names) or 2,3-dihydro-1,4-benzodioxin (new systematic name)) is one of many benzene annulated oxygen O-heterocycles [29].…”