5-肼基四唑高氯酸含能配合物的合成、表征及性能  

Synthesis,Characterization and Properties of Perchlorate Complexes with 5-Hydrazinotetrazole as Ligand

作　　者：张至斌 张建国[1] 许彩霞[1] 殷昕[1] 何飘[1] 

机构地区：[1]北京理工大学爆炸科学与技术国家重点实验室,北京100081

出　　处：《含能材料》2016年第1期53-59,共7页Chinese Journal of Energetic Materials

基　　金：国家自然科学基金委-中国工程物理研究院联合基金(NSAF10776002)

摘　　要：以5-肼基四唑(5-HT)为配体,制备5种含能配合物[Cd(HT)_6](ClO_4)_2(1),[Zn(HT)6](ClO_4)_2(2),[Ni(HT)_3](ClO_4)_2(3),[Co(HT)_6](ClO_4)_2(4),[Mn(HT)_6](ClO_4)_2(5)。采用元素分析和傅里叶变换红外光谱对5种配合物进行结构表征。通过差示扫描量热分析(DSC)研究其热分解性能,测试了其摩擦感度和撞击感度。在B3LYP/6-311++g**水平上理论研究了5-HT电子结构性质、自然键轨道电荷以及分子前线轨道。结果表明,5种配合物具有较高热稳定性,分解温度均高于200℃。5-HT四唑环上的N(3)和N(4)原子更容易同时参与金属原子配位,形成以5-肼基四唑为配体的配位化合物。90°摆角、1.96 MPa条件下,配合物4的摩擦感度为96%,800 g落锤下,撞击感度H50为25 cm,其机械感度与肼基四唑汞(HTMP)和高氯酸·四氨·双(5-硝基四唑)合钴(Ⅲ)(BNCP)相当,有望应用于起爆药领域。Five coordination complexes [Cd（HT）61 （CLO4）2（1）, [Zn（HT）6J （C[O4）2（2）, [Ni（HT）3] （CIO4）2（3）, [Co（HT）6] （CIO4）2（4） , [ Mn（HT）6] （CIO4）2（5） with 5-hydrazinotetrazole （5-HT） as ligands were prepared. Their structures were characterized by elemental analysis and FT-IR. The thermal decompositions were studied by differential scanning calorimetry and the impact sensitivity and friction sensitivity were also tested. The theoretical calculations of the electronic structure, natural bond orbital charge and frontier orbital energy of 5-HT were studied at B3 LYP/6-311 ＋＋g^＊＊ level. Results show that the five complexes have good thermal stability, and the decomposition temperatures are above 200 ℃. N （3） and N （4） atoms of tetrazole ring are easier to coordinate with metal atoms. The friction sensitivity of complex 4 is 96% （90°, 1.96 MPa） and H50 is 25 cm with the 800 g drop hammer, which is similar to that of HTMP and BNCP, indicating a promising application in the field of primary explosive.

关 键 词：含能配合物 5·肼基四唑(5-HT) 合成表征 热分析 电子结构 机械感度 

分 类 号：TQ560.1[化学工程—炸药化工]