ADN/PDO共晶高效制备与结构和性能表征  

Efficient Preparation of ADN/PDO Cocrystal and Characterization of the Structure and Properties

作　　者：刘泽宁 乔申 马凡 杨宗伟[2] 于雁武 LIU Ze-ning;QIAO Shen;MA Fan;YANG Zong-wei;YU Yan-wu(School of Environment and Safety Engineering,North University of China,Taiyuan 030051,China;Institute of Chemical Materials,CAEP,Mianyang 621999,China)

机构地区：[1]中北大学环境与安全工程学院,山西太原030051 [2]中国工程物理研究院化工材料研究所,四川绵阳621999

出　　处：《含能材料》2024年第12期1314-1320,共7页Chinese Journal of Energetic Materials

基　　金：国家自然科学基金(22275175和21975233);中华人民共和国公安部重点实验室基金(2023FMKFKT01)。

摘　　要：为了开发一种快速高效且绿色环保的二硝酰胺铵/吡嗪‐1,4‐二氧化物(ADN/PDO)共晶制备新途径并表征其性能,采用反应结晶法,以纯水作为溶剂,制备了ADN/PDO共晶,采用光学显微镜(OP)、单晶X射线衍射(SXRD)以及粉末X射线衍射(PXRD)对共晶的形貌和结构进行表征。结果显示,ADN/PDO共晶晶体呈棱柱状,由ADN和PDO分子按摩尔比2∶1结合形成,室温下晶体密度为1.779 g·cm^(-3),属于单斜晶系,空间群为P21/c。通过DSC测试和增重法对ADN/PDO共晶的热性能和吸湿性进行了表征,并使用NASA CEA对能量性能进行预测。研究表明,采用该方法制备的ADN/PDO共晶的熔点为113.3℃,比ADN提高了21.3℃,分解温度略高于ADN,具有较好的热稳定性。共晶的吸湿率仅为2.6%,大幅度降低了ADN(45%)的吸湿性。此外,经NASA CEA软件计算得到共晶的理论比冲高达277.9 s,优于ADN(197.5 s),具有较高的能量。因此,反应结晶法实现了高能量低吸湿的ADN/PDO共晶高效制备,为进一步评估其应用性能奠定了基础。Herein,we develop a new method to prepare the ammonium dinitramide/pyrazine-1,4-dioxide(ADN/PDO)cocrystal,which is highly efficient and environmental-friendly due to utilizing the reaction crystallization with pure water as the solvent,and also comprehensively characterized its performance.The morphology and structure of the cocrystal were characterized by optical microscopy(OP),powder X-ray diffraction(PXRD),and single crystal X-ray diffraction(SXRD),respectively.In detail,the ADN/PDO cocrystal was prismatic and formed by the combination of ADN and PDO molecules at a molar ratio of 2∶1.Moreover,the ADN/PDO cocrystal belongs to the monoclinic crystal system with a space group of P21/c,owning a theoretical density of 1.779 g·cm^(-3)at room temperature.Furthermore,through the differential scanning calorimetric(DSC)measurement,it turned out that the melting point of the prepared ADN/PDO cocrystal is 113.3℃,which is 21.3℃higher than that of ADN,and the decomposition temperature is slightly higher than that of ADN,demonstrating good thermal stability of the prepared ADN/PDO cocrystal.Then,the hygroscopicity of the prepared cocrystal,measured by the weight increment method,is significantly low at only 2.6%,while that of ADN is at 45%.In addition,calculated by the NASA CEA,the theoretical specific im-pulse of the cocrystal reaches 277.9 s while that of ADN is 197.5 s,demonstrating the high energy performance of the cocrystal.In conclusion,the reported method based on the reaction crystallization successfully enables the efficient production of a high-energy,low-hygroscopic ADN/PDO cocrystal,thereby facilitating the further assessment of its application performance.

关 键 词：二硝酰胺铵(ADN) 共晶 吸湿性 吡嗪‐1 4‐二氧化物(PDO) 

分 类 号：TJ55[兵器科学与技术—军事化学与烟火技术] O62[理学—有机化学]