Theoretical Study on Energetic Materials Containing (Difluoramino)dinitromethyl Substituted Heteroaromatic Rings
Received date: 2024-01-16
Online published: 2024-03-04
Supported by
National Natural Science Foundation of China(22175197); Strategic Priority Research Program of the Chinese Academy of Sciences(XDB0590000)
In recent decades, the development of traditional energetic materials has encountered a bottleneck. How to continue to improve the energy level and break the bottleneck has become an urgent problem in the field of energetic materials. Fluorine is a stronger oxidizing agent than oxygen, and theoretically the introduction of fluorine can further increase energy density. Thirteen kinds of energetic molecules containing (difluoramino)dinitromethyl substituted heteroaromatic rings were designed. To ensure the possibility of synthesis, all the structural designs are based on existing intermediates and could be transformed into target molecules through mature synthesis methodologies. The molecular structure, initial thermal decomposition mechanism and energy characteristics were studied theoretically with density functional theory (DFT) methods (B3LYP/6-311+G(d,p) and M06-2X/6-311+G(d,p)) using Gaussian16 program. By calculating the mechanism of the initial decomposition reaction, the trigger bond was determined to be one of the C—NO2 bonds in the (difluoramino)dinitromethyl group. Dynamic stability is evaluated by the energy barrier of the trigger bond breaking. The results show that most of these molecules have sufficient dynamic stability, the initial decomposition reaction barriers are around 30 kcal/mol. The relationship between the molecule structure and the dynamic stability is revealed. The carbon radical center in the transition state is connected with the strong electron-withdrawing groups (-NO2 and -NF2) and the heterocyclic ring with a certain electron-donating ability. This is a typical “push-pull” electronic structure, which makes the free radical particularly stable. Therefore, the homo-cleavage energy barrier of the trigger bond is determined by the stabilizing effect of heterocyclic rings on the methyl free radicals. The energy properties of these molecules were theoretically evaluated with nitrate ester plasticized polyether (NEPE) solid propellant formulations using EXPLO5 program. The results show that the specific impulse of one dynamic stable molecule is up to 280.1 s, which is about 8.4 s higher than that of the traditional HMX (Octogen) formulations.
Yongkang Cui , Shoufei Cheng , Lin Ling , Yuxue Li , Long Lu . Theoretical Study on Energetic Materials Containing (Difluoramino)dinitromethyl Substituted Heteroaromatic Rings[J]. Acta Chimica Sinica, 2024 , 82(4) : 377 -386 . DOI: 10.6023/A24010017
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