复合型含能基团结构和性能的理论研究

doi:10.6023/A26040105

摘要/Abstract

打破含能材料的发展瓶颈,是近年来亟待攻克的难题. 本文尝试从设计新型含能基团的角度来探索新含能分子. 通过将传统含能基团进行组合,使用DFT方法计算了分子结构、初始热分解机理,使用KJ方程和EXPLO5计算了爆轰性能,筛选出39个含能基团,初始分解能垒≥30kcal/mol。其中5个已有实验合成的结构在热稳定性方面,计算结果和实验十分吻合。尝试用烷烃和多胺骨架进行分子设计,所得分子密度>2.0g/cm³,爆速>8000 m/s,爆压>33 GPa. 分子内张力/位阻、以及N原子孤对电子的超共轭效应,对最终含能分子的动力学稳定性具有重要影响。

关键词: 复合型含能基团, 含能材料, 分子设计, 理论研究, 动力学稳定性

Breaking the development bottlenecks of traditional energetic materials has become an urgent problem to be solved in recent years. In general, energetic materials are composed of energetic groups and molecular skeletons. At present, most design strategies for energetic molecules focus on the construction of novel molecular skeletons. Inspired by the unconventional complex energetic groups reported in the literature, this study focused on the design of new “composite energetic groups”. A total of 72 initial structures were obtained by combining traditional energetic groups. Theoretical calculations on their molecular structures, initial thermal decomposition mechanisms were performed via density functional theory (DFT) using the Gaussian16 program. Excellent kinetic stability ensures a sufficiently high thermal decomposition temperature and favorable chemical stability, which are essential prerequisites for the practical application of energetic molecules. Identifying accurate trigger bonds and reliable decomposition mechanisms is critical for determining the initial decomposition energy barriers. Multiple potentially fractured chemical bonds and various cleavage pathways were considered, including homolysis, heterolysis, group migration, and elimination. The Kamlet-Jacobs (KJ) equation and the EXPLO5 program were adopted to calculate detonation velocity and detonation pressure. Subsequently, 39 energetic groups were screened out based on energetic performance and kinetic stability, all possessing an initial decomposition energy barrier of ≥30 kcal/mol, among which 34 were unprecedented new groups. For five experimentally synthesized structures, detailed comparisons demonstrated that the calculated thermal stability results were in excellent agreement with experimental data. Furthermore, molecular design was carried out using alkane skeletons and polyamine skeletons. It is revealed that the intramolecular strain and steric hindrance dominated by alkane skeletons, as well as the hyperconjugation effect, exert a significant influence on the kinetic stability of the final energetic molecules. All these molecules exhibit a density >2.0 g/cm³, a detonation velocity >8000 m/s, and a detonation pressure >33 GPa.

Key words: composite energetic groups, energetic materials, molecular design, theoretical study, kinetic stability

引用此文

马玲玲, 凌琳, 李玉学, 吕龙. 复合型含能基团结构和性能的理论研究[J]. 化学学报, doi: 10.6023/A26040105.

Ma Lingling, Ling Lin, Li Yuxue, Lu Long. Theoretical Study on the Structure and Properties of Composite Energetic Groups[J]. Acta Chimica Sinica, doi: 10.6023/A26040105.

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