【作者】 李欣；

【导师】 陈三平；

【作者基本信息】 西北大学 ， 无机化学， 2017， 硕士

【摘要】 改善固体推进剂的燃烧性能及提高固体推进剂的能量水平一直是各国研究人员致力解决的问题。近几年,含能配合物作为燃烧催化剂吸引了的兴趣,其中能量配体保证自身具有高的能量,金属中心使其具有好的催化活性。富氮杂环蕴含着大量的能量,硝基的引入可以进一步促进能量的释放。基于以上考虑,本论文选取4,5-二四唑基^-1,2,3-三唑（H3ddt）和3,3’-二硝基-5,5’-联^-1,2,4-三唑（H2dnbt）为能量配体,通过水热/溶剂热法,构建了六个含能配合物:{[Zn（Hddt）（H₂O）2]·H₂O}n（1）、[Cu₃（ddt）₂（H₂O）2]n（2）、[Co（dnbt）（H₂O）4]ClO₄（3）、[Cu₂（dnbt）₂（H₂O）₃（CH₃OH）]·3H₂O（4）、[Pb（dnbt）（H₂O）₃]n（5）、[Ag₈（dnbt）₄]_n（6）。表征了六个配合物的结构和理化性质,研究了其作为燃烧催化剂对固体推进剂燃烧性能的影响。主要研究内容如下:1.利用X-射线单晶衍射仪对1-6的结构进行表征。结构分析表明,H3ddt在不同的条件下可以展现不同的配位模式;在1中,以部分脱质子的形式(Hddt^2-)与Zn（Ⅱ）形成一维的链状结构;在2中配体以完全脱质子的形式（ddt3-）与Cu（Ⅱ）形成三维框架结构。H2dnbt在3-6中均以dnbt^2-配离子的形式参与配位,但是由于Ag（Ⅰ）/Pb（Ⅱ）和氧原子具有强的亲和力,所以在5、6中,硝基上的氧原子也参与了配位。随着更多配位点的配位,3-6的维度也随之提高（3、4为零维、5为一维、6为三维）。2.结合TG-DSC热分析仪研究了六个配合物的热分解行为。结果表明,六个配合物均具有高的热稳定性,其中5、6的热分解温度超过300℃。采用Kissinger’s和Ozawa-Doyle’s方法,研究了六个配合物的非等温动力学、计算了表观活化能和指前因子。3.利用本课题组特有的精密转动弹热量计准确获得了配合物1-6的恒容燃烧热,并计算得到了配合物的标准摩尔生成焓。根据K-J方程估算了配合物的爆轰性能,其爆热、爆压、爆速范围分别为 0.78^-1.76 kcal·g^-1、31-39 GPa、8000-8400 m·s^-1。同时,感度测试发现,六个配合物的撞击感度均大于40 J、摩擦感度均大于360 N。4.利用DSC研究了六个配合物对高氯酸铵（AP）、二硝酰铵（ADN）的热分解影响,结果表明2和4对AP具有明显的催化作用,可将AP缓慢的两步分解过程合并为一步剧烈的快速分解过程。当2、4与AP的质量比为1:3时,分解峰温分别提前至325℃和319℃。4对ADN具有很高的催化活性,催化剂的加入量仅为2%,也可使分解峰温提前19.2℃。更多还原

【Abstract】 The researchers have been devoted to improve the combustion performance and the energy level of solid propellants.In recent years,energetic complexes as a combustion catalyst have attracted the interest of researchers,in which energy ligands would ensure them with high energy and the metal center would provide good catalytic activity.Nitrogen-rich heterocycles contain a lot of energy,the introduction of nitro into nitrogen-rich heterocycles can further accelerate the release of energy.Based on the above considerations,six energetic complexes:{[Zn（Hddt）（H₂O）2]·H₂O}n（1）、[Cu₃（ddt）₂（H₂O）2]n（2）、[Co（dnbt）（H₂O）4]ClO₄（3）、[Cu₂（dnbt）₂（H₂O）₃（CH₃OH）]·342O（4）、[Pb（dnbt）（H₂O）₃]n（5）、[Ags（dnbt）4]n（6）were synthesized with 4,5-di（1H-tetrazol-5-yl）-2H^-1,2,3-triazole（H3ddt）and 3,3’-dinitro-5,5’-bis(1H^-1,2,4-triazole)（H2dnbt）as energy ligands by hydro/solvothermal method.The structures and physicochemical properties of the 1-6 were characterized.The effect of 1-6 on the combustion of the solid propellant were studied.The main research contents are as follows:1.The structure analysis shows that H3ddt can exhibit different coordination modes under different conditions.Zn（Ⅱ）and Hddt^2-forms a one-dimensional chain structure in 1;while ddt3-and Cu（Ⅱ）to form a three dimensional framework structure in 2.H2dnbt has the some form(dnbt^2-)in 3-6,the oxygen atoms of the nitro groups also participated in the coordination in 5 and 6,due to Ag（Ⅰ）/Pb（Ⅱ）and oxygen atoms have strong affinity.With the coordination of more coordination sites,the dimensions of 3-6 are gradually increased(3/4-0D,5^-1D,6-3D).2.The thermal decomposition behavior of 1-6 were studied by TG-DSC.The results show that the six complexes have high thermal stability,and the thermal decomposition temperature of 5 and 6 exceeds 300℃.Combined with Kissinger’s and Ozawa-Doyle’s methods,the non-isothermal kinetics of 1-6 were studied,and the apparent activation energies and pre-exponential factors were calculated.3.The constant volume energy of combustion of 1-6 were measured by a rotating-oxygen bomb calorimeter,which were used to calculate the standard molar enthalpy of formation.According to the K-J equation,the detonation performances of 1-6 were estimated.The heats of detonation,detonation pressure and detonation velocity ranges from 0.78 to 1.76 kcal·g^-1,31-39 GPa,8000-8400 m·s^-1,respectively.At the same time,the sensitivity test found that the impact of 1-6 were greater than 40 J,the friction sensitivity is greater than 360 N.4.The effects of complexes on the thermal decomposition of ammonium perchlorate（AP）and ammonium dinitramide（ADN）were studied by DSC.The results showed that 2 and 4 have obvious catalytic effect on thermal decomposition of AP,which can convert the slow decomposition process of pure AP to a rapid decomposition process.When the mass ratio is 1:3（2/4:AP）,the decomposition peak temperature can drop to 325℃ and 319℃,respectively.4 has high catalytic activity for ADN,when the addition of catalyst is only 2%,the decomposition peak temperature can reduce 19.2℃.更多还原