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含能材料  2015 

四硝基甘脲的合成工艺改进及热分析

DOI: 10.11943/j.issn.1006-9941.2015.05.007

Keywords: 含能材料 四硝基甘脲 甘脲 硝化 热分解

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Abstract:

以尿素和乙二醛为原料, 在盐酸催化下经微波加热制得甘脲(GU), 用发烟硝酸醋酐对GU硝化合成了四硝基甘脲(TNGU)。考察了反应温度、反应时间和发烟硝酸用量等对硝化反应过程的影响。采用红外光谱、核磁共振光谱及元素分析对TNGU结构进行了表征, 用DSC对其进行了热分析, 用Kissger和Ozawa法确定了TNGU的反应动力学参数, 估算了热爆炸临界温度(Tb)及热分解反应的活化熵变(ΔS≠)、活化函变(ΔH≠)和活化吉布斯自由能变化值(ΔG≠)。结果表明, TNGU的较佳合成工艺条件为: GU 5 g时, 发烟硝酸70 mL, 醋酸酐35 mL, 反应温度25~30 ℃, 反应时间4 h, TNGU收率为84%(以GU计)。此工艺较文献废酸液量减少30 mL, 硝化时缩短4 h。TNGU的Tb为465.34 K, ΔS≠、ΔH≠和ΔG≠分别为171.46 J·mol-1、195.00 kJ·mol-1和194.99 kJ·mol-1, TNGU的热分解为放热熵增的过程

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