二氨基二硝基吡啶氮氧化物耐热与钝感机理研究

In order to study heat-resistance and desensitizing mechanism of 2,6-diamino-3,5-dinitropyridine-1-oxide(ANPyO), thermal decomposition products and molecular configuration of ANPyO were investigated, and heat-resistance and desensitizing mechanism of ANPyO were determinated, using thermal analysis testing and calculation analysis and quantum chemistry calculation method of molecular configuration. The ANPyO-based polymer bonded explosive(PBX) moulding powders were manufactured with nitrile-butadiene rubber and fluorine rubber as binder by means of solution-water suspending-distillation method, ANPyO/nitramine explosive composites were prepared by crystal coating and mixing method respectively. The structures and properties of ANPyO and the samples were characterized by micro-morphology, coating effect, thermal analysis, laser particle size analysis, heat-resistance, energy and safety tests, etc. The heat-resistance and desensitizing mechanism and its difference of ANPyO in PBX moulding powders and ANPyO/niramine explosive composites were analysed by comparing the structure and property differences of PBX moulding powders and ANPyO/niramine explosive composites, technique and formula of better heat-resistance and desensitizing efficiency were defined, they can provide correlative theoretical reference for the use of ANPyO as a new heat-resistance desensitivity energetic materials.

为了研究2,6-二氨基-3,5-二硝基吡啶-1-氧化物(ANPyO)的耐热与钝感机理，用热分析测试及其计算与分子构型量子化学计算的方法，对ANPyO热分解产物和分子构型进行分析，确定其耐热与钝感机理。用溶液-水悬浮-蒸馏法制备ANPyO与橡胶类(氟橡胶和丁腈橡胶)黏结剂的高聚物黏结炸药(PBX)造型粉样品；用不同的工艺方法制备ANPyO与硝胺炸药的复合物样品。采用微观形貌、包覆度、热分析、激光粒径分析、耐热性、能量与安全性等分析测试手段表征ANPyO及其制备样品的结构与性能。通过比较不同PBX和复合物结构与性能的差别，确定PBX和复合物中ANPyO的耐热与钝感机理并比较其差别，确定耐热性或安全性较好的配方及工艺方法。为ANPyO作为一种新型耐热钝感含能材料的应用拓展提供相关的理论参考。

2,6-二氨基-3,5-二硝基吡啶-1-氧化物(ANPyO)具有优良的耐热和钝感性能，能够满足石油深井开采和宇宙航行等特殊需要，也能够作为新型含能钝感剂在不明显影响硝胺炸药能量水平的前提下有效降低其感度，其作为新型高能量密度材料得到了国内外的广泛关注。在国家自然科学基金青年基金的资助下，热分析测试及其计算分析与分子构型量子化学计算的方法，对ANPyO热分解产物和分子构型进行分析，确定其耐热与钝感机理。采用不同的分析测试手段表征ANPyO及其制备样品的结构与性能，分析比较其差别并研究其相互作用机理。所取得的主要研究成果：（1）研究了ANPyO的热分解历程，获得了ANPyO热分解动力学参数、分解机理函数和分解机理；（2）研究了ANPyO及其复合物的热分解性能，获得了整个热分解过程中压力、温度和温升速率随时间的变化曲线，通过温升速率方程计算获得了动力学参数；（3）研究了ANPyO对硝胺炸药感度的影响，比较了不同工艺方法、黏结剂种类及含量等因素对硝胺炸药性能的影响并进行相关分析；（4）研究了ANPyO及其配方的耐热性能并进行相关耐热机理分析，通过不同的方法比较了常用单质耐热炸药的耐热性能，得出了相关结论；（5）优化了ANPyO分子构型，对安全性能进行理论计算，获得了能带结构和态密度、原子电荷、重叠集居数、晶格能等参数（6）研究和改进了耐热性测试装置，开发出一种安全可靠、性能稳定温控温耐热性检测装置，实现长达数天时间内准确测量不同温度下样品的耐热性。迄今为止，已在国内外核心期刊上发表署名国家自然科学基金项目资助的研究论文5篇，申请国家发明专利3项，参加国内学术会议6人次；已经培养博士研究生1名，硕士研究生3名，1名项目团队成员晋升高一级职称。