Zr(BHT)_2高能钝感燃烧催化剂的合成及热分解行为

Synthesis and Thermal Decomposition Behavior of Zr(BHT)_2 High Energy Insensitive Combustion Catalyst

以二氯乙二肟、二甲基甲酰胺、叠氮化钠、盐酸羟胺和硝酸锆等为原料,采用络合沉淀法合成了高能钝感的Zr(BHT)_2燃烧催化剂;利用差示扫描量热法(DSC)和热重法(TG)研究了不同升温速率下Zr(BHT)_2的热分解性能;分别利用Ozawa法和Kissinger法计算其表观活化能(EO和EK)和指前因子(Ak),得到其热分解动力学参数、热分解机理函数、热爆炸温度和热力学性质;测试了其撞击感度和摩擦感度。结果表明,Ozawa法和Kissinger法计算得到Zr(BHT)_2的表观活化能分别为150.51和152.15kJ/mol,热分解过程符合Avrami-Erofeev方程;自加速分解温度和热爆炸临界温度分别为497.63和530.71K;热分解自由能(ΔG~≠)为122.04kJ/mol,活化焓(ΔH~≠)为147.88kJ/mol,活化熵(ΔS~≠)为50.27J/mol。感度测试结果表明,Zr(BHT)_2燃烧催化剂对撞击和摩擦均钝感,安全性较高。

High energy insensitive combustion catalyst Zr（BHT）; was synthesized by complexing precipitate method using dichloro ethylene dioxime, dimethylformamide, sodium azide, hydroxylamine hydrochloride and zirconium nitrate as raw materials. The thermal decomposition properties of Zr（BHT）; were studied by differential scanning calorimetry （DSC） and thermogravimetry （TG） at different heating rates. The apparent activation energies （EK and Eo） and pre exponential constant （Ak） were calculated by Ozawa＇ s method and Kissingef s method. The kinetic parameters and mechanism function of thermal decomposition, thermal explosion temperature and thermodynamic parameters were obtained, and the impact sensitivity and friction sensitivity were measured. The results show that the apparent activation energies of Zr（BHT） by Ozawa and Kissinge{s method were 150. 51 and 152. 15 kJ/mol, respectively, and the thermal decomposition is in accordance with Avrami Erofeev equation. The selPaccelerating decomposition temperature and the critical temperature of thermal explosion are 497.63 and 530.71 K, respectively. The free energy of activation of thermal decomposition reaction （/kG#） is 122.04 kJ,/mo], the enthalpy of activation （△H≠） is 147.88 kJ/mol, and entropy of activation （AS≠） is 50. 27 J/tool. The sensitivity test results also show that Zr（BHT）; combustion catalyst is insensitive to impact and friction, and the safety is relatively high.