Acta Chimica Sinica ›› 2024, Vol. 82 ›› Issue (4): 377-386.DOI: 10.6023/A24010017 Previous Articles     Next Articles

Original article

二氟氨基二硝甲基芳香杂环含能材料的理论研究

崔勇康a,b, 成守飞a,b, 凌琳b, 李玉学b,*(), 吕龙b,*()   

  1. a 上海理工大学材料与化学学院 上海 200093
    b 中国科学院上海有机化学研究所 先进氟氮材料重点实验室(中国科学院) 上海 200032
  • 投稿日期:2024-01-16 发布日期:2024-03-04
  • 基金资助:
    国家自然科学基金(22175197); 中国科学院战略性先导科技专项(XDB0590000)

Theoretical Study on Energetic Materials Containing (Difluoramino)dinitromethyl Substituted Heteroaromatic Rings

Yongkang Cuia,b, Shoufei Chenga,b, Lin Lingb, Yuxue Lib,*(), Long Lub,*()   

  1. a School of Materials and Chemistry, University of Shanghai for Science and Technology, Shanghai 200093, China
    b Key Laboratory of Fluorine and Nitrogen Chemistry and Advanced Materials, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, China
  • Received:2024-01-16 Published:2024-03-04
  • Contact: * E-mail: liyuxue@sioc.ac.cn; lulong@sioc.ac.cn
  • 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.

Key words: difluoramino compound, energetic material, solid propellant, specific impulse, theoretical research