含能配位聚合物Pb(BTO)(H2O)n的合成、结构与性能

摘要

以5,5′-联四唑-1,1′-二羟基二水化合物(H2BTO·2H2O)与Pb(NO3)2为原料,采用简单的一步溶剂热法合成了一种配位聚合物[Pb(BTO)(H2O)]n(BTO=5,5′-联四唑-1,1′-二氧化合物).用X射线单晶衍射、傅里叶变换红外光谱及元素分析对目标化合物进行了表征.利用差热分析(DTA)、差示扫描量热分析(DSC)和热重-微分热重分析(TG-DTG)研究了该含能配位聚合物的热分解过程.采用Kissinger法和Ozawa法分别计算了其热分解动力学参数(活化能EK、EO、指前因子A).用WL-1型撞击感度测试仪测定了[Pb(BTO)(H2O)]n的特性落高H50,采用DTA分析了其对高氯酸铵(AP)热分解的催化性能.结果表明,该晶体属于单斜晶系,C2/c空间群,a=14.342(3) (A),b=6.5757(12)(A),c=8.4715(16)(A),V=683.3(2)(A)3,Dc=3.823 g·cm-3,Z=4.在5 K·min-1的 DSC曲线上,其分解峰值温度为582.2 K,TG曲线上存在三个质量损失阶段,主要质量损失阶段位于543.9~599.5 K,最终剩余残渣质量为44.60 %.EK=211.67 kJ·mol-1,EO=210.64 kJ·mol-1,ln(A/s-1)=18.594,H50=7.6 cm,显示其具有较好的热稳定性和适当的感度.该配位聚合物添加量为10%时,AP的高温分解峰提前40.1 K,而且热分解反应的激烈程度也大大提高,对AP表现出良好的催化性能.%An energetic coordination polymer, [Pb(BTO)(H2O)]n (BTO=1H,1′H-5,5′-bistetrazole-1,1′-diolate) was synthesized by a simple one-step solvothermal method using Pb(NO3)2 and H2BTO·2H2O as raw materials.The target compound was characterized by single-crystal X-ray diffraction, Fourier transform infrared (FT-IR) spectra and elemental analysis.The thermal decomposition process of the energetic coordination polymer was studied by differential thermal analysis (DTA), differential scanning calorimetry (DSC) and thermogravimetry-derivative thermogravimetry (TG-DTG).Its kinetic parameters of thermal decomposition (activation energy EK、EO and pre-exponential factor A) were calculated by Kissinger′s method and Ozawa′s method.Its characteristic drop height of impact sensitivity (H50) was determined by WL-1 type impact sensitivity test instrument.The compound was explored as additive to promote thermal decomposition of ammonium perchlorate (AP) by DTA.Results show that the crystal belongs to monoclinic, its space group is C2/c with crysta parameters of a=14.342(3) (A), b=6.5757(12) (A), c=8.4715(16) (A), V=683.3(2) (A)3, Dc=3.823 g·cm-3, Z=4.Its thermal decomposition temperature on DSC curve at 5 K·min-1 is 582.2 K, there are three mass loss stages on TG curve with a main mass loss between 543.9 K and 599.5 K, the mass of the final residue is 44.60%.EK=211.67 kJ·mol-1, EO=210.64 kJ·mol-1, ln(A /s-1)=18.594, H50=7.6 cm, revealing that it has better thermal stability and appropriate sennsitivity.When the addition amount of the coordination polymer is 10 wt%, the high temperature decomposition peak of AP is decreased by 40.1 K, the intense degree of the thermal decomposition reaction is also greatly improved, showing that it has good catalytic performance to AP.