硅烷偶联剂与TATB分子间相互作用的理论研究  

Theoretical Study on Intermolecular Interactions and Coupling Mechanism between Coupling Agent and TATB

作　　者：张艳丽[1,2] 姬广富[3] 常兰[1,2] 

机构地区：[1]成都理工大学工程技术学院,四川乐山614000 [2]核工业西南物理研究院,四川成都610041 [3]中国工程物理研究院流体物理研究所冲击波物理与爆轰物理国防重点实验室,四川绵阳621999

出　　处：《含能材料》2015年第2期135-139,共5页Chinese Journal of Energetic Materials

基　　金：国防基础科研项目(B1520110002);中国工程物理研究院科学技术发展基金(2013B0101002)

摘　　要：利用密度泛函理论LDA/PW方法对γ-氨基丙基三醇硅烷(KH5501)偶联剂和1,3,5-三氨基-2,4,6-三硝基苯(TATB)分子间相互作用及其偶联机制进行了理论研究。结果表明硅烷偶联剂与TATB分子间的相互作用,改变了TATB分子的平面结构,增强了TATB分子的C—NO2键强度,降低了TATB分子的光热稳定性。另外,计算结果还表明硅烷偶联剂羟基上的氢与TATB硝基上的氧之间形成的氢键作用是硅烷偶联联剂与TATB发生偶联作用的主要形式,这一结论与实验预测结果一致。The intermolecular interactions between γ-aminopropyltrianolsilane （KH5501） and TATB were theoretically studied using the density functional theory LDA/PW method and the three optimized geometries of the mixture of KH5501and TATB were obtained. By analyses of bond length and bond angles of TATB before and after mixing with KH5501 , It is found that the coupling agent KH5501 changes the structure of TATB in two was： the bond length of C-NO2 bond is shortened, and accordingly, the impact sensitivty decreases. In another side the planar structure of TATB is destroyed and accordingly, the molecular polarity of TATB is enhanced. The analyses of the frontier orbits of TATB show that, the interaction between KH5501 and TATB, make the gaps of frontier orbits become narrower, thereby the thermostability as well as the photostability of TATB is debased, and the reac- tion activity of TATB is enhanced. Through the comparation of the calculation results between three optimized geometries, the results indicate that the bond length of N-O bond of TATB all get longer, particularly, the 1V geometry gets longest. Although the electron transfer between TATB and KH5501 occur, the IV geometry transfers largest. Meanwhile, compared with other geometries, there is the largest energy of the molecular interaction in IV geometry. For mentioned above reasons, it is concluded that the IV geometry is of the largest stability among the three geometries, and the main bonding between TATB and KH5501 in IV geometry is the hydrogen bond interactions formed between the hydrogen atom in the hydroxide of KH5501 and the oxygen atom in the nitric of TATB. It is the hydrogen bond interactions, formed between the hydrogen atom in the hydroxide of KH5501 and the oxygen atom in the nitric of TATB, that improve the binding and the interfacial properties of TATB, which is consistent with the experimental results.

关 键 词：分子间相互作用 偶联机理 LDA/PW方法 1 3 5-三氨基-2 4 6-三硝基苯(TATB) 硅烷偶联剂 

分 类 号：TQ560.1[化学工程—炸药化工]