【作者】 王伟涛；

【导师】 高胜利； 陈三平；

【作者基本信息】 西北大学 ， 无机化学， 2010， 硕士

【摘要】 四唑属富氮且稳定性较好的化合物,.是目前研究较多的高能钝感含能材料。杂环中的四个氮原子均可提供配位点,配合物赋有多种配位模式,从而使其成为制备含能配合物的一类重要配体。本论文以5,5’-氨基双四唑和5,5’-偶氮双四唑为配体,以金属铅、过渡金属及镧系金属为中心金属,用溶液法和溶剂热法合成了十七种含能配合物,利用元素分析、红外、X-射线单晶衍射、TG和DSC技术研究了它们的组成、结构及热稳定性等性质。研究发现,双四唑配体在配合物中表现出了丰富的配位模式,并且在本论文中出现了未见文献报道的三种配位模式：μ3-1,1’：3：3’,μ3-1,1’：3：4’,μ3-1,1’：4：4’；配合物的热稳定性较好,配合物[Co(bta)(en)2][NO3](4)和[Cu(bta)(en)]n(5)可以在280℃之前稳定存在。通过DSC技术研究了配合物对高氯酸铵(AP)的热分解的影响。利用四种不同的升温速率下的配合物与AP组成的二元混合体系的DSC曲线,用Kissinger法计算了其热分解参数。通过对比不同二元混合体系与AP的表观活化能、指前因子与分解峰温,并与配合物的结构及配合物中的金属离子关联,研究发现,具有复杂三维结构的配合物比简单零维结构的配合物有较好的催化效果；氨基双四唑的配合物中,铅配合物的催化性能较钴和铜的催化性能好；不同的镧系金属的双四唑配合物的催化效果类似。更多还原

【Abstract】 Tetrazole is the unsaturated energetic heterocyclic compound with high nitrogen content and good stability leading to the high energy yet low sensitivity materials. Additionally, the four nitrogen atoms in the tetrazole provide the coordination points to form the complexes, which prossess variable coordination modes. Therefore, the tetrazole is the important ligand from the aspect of coordination chemistry.In this thesis, we chose the bis-(tetrazolyl)amine and the 5,5’-azoetrazoeate as the ligands, and employed the metal lead, transition metals and lanthanide metals as the center metals, via the solution method and solvothermal method, synthesis 17 kinds of energetic complexes. Furthermore, the elemental analysis, IR spectroscopy, X-ray diffraction and TG-DSC techniques were employed to determine their formula, study the structure and thermal stability. And we found that the bistetrazole as the ligand in the complex exhibited abundant coordination modes including three unreported new modes shown in as-synthesized complexes; as-synthesized complexes in this thesis prossessed good thermal stability and complexes [Co(bta)(en)2][NO3](4) and [Cu(bta)(en)]n (5) even could be stable up to 280℃.The effects of as-synthesized complexes on the thermal decomposition of ammonium perchlorate (AP) were studied by the DSC techniques. The thermal decomposition parameters of the binary mixture systems were calculated by the Kissinger method through the DSC curves at four different heating rates. According to the apparent activation energy, pre-exponential factors and the temperature of thermal decomposition peaks related to the structures and different metals, it is indicated that the complicated 3D polymeric complex exhibits better catalysis than the OD complex; the bis-(tetrazolyl)amine complexes with lead ion are better than the metal of copper and cobalt complexes; different lanthanide metal complexes show the similar catalysis effects on the thermal decomposition of AP.更多还原