CL⁃20/HMX共晶在有机溶剂中的三元相图测定  

Determination of ternary phase diagram of CL-20/HMXcocrystal in pure solvent

作　　者：杨秋秋 强福智[2] 徐胜良[2] 张慧琴[2] 赵华丽[2] 王亮[2] 谭利敏 刘发龙[2] YANG Qiuqiu;QIANG Fuzhi;XU Shengliang;ZHANG Huiqin;ZHAO Huali;WANG Liang;TAN Limin;LIU Falong(National Key Laboratory of Aerospace Chemical Power,Xiangyang 441003,China;Hubei Institute of Aerospace Chemotechnology,Xiangyang 441003,China)

机构地区：[1]航天化学能源全国重点实验室,襄阳441003 [2]湖北航天化学技术研究所,襄阳441003

出　　处：《固体火箭技术》2025年第1期42-47,共6页Journal of Solid Rocket Technology

基　　金：国家自然科学基金(22275051)。

摘　　要：为深入分析六硝基六氮杂异伍兹烷(CL-20)/奥克托金(HMX)共晶炸药形成过程及其溶解行为,采用高效液相色谱法测定了HMX、CL-20分别在丙酮、乙腈和二甲基亚砜(DMSO)中的溶解度以及HMX在不同浓度CL-20溶液中的溶解度,构建了20℃下CL-20/HMX/丙酮、CL-20/HMX/乙腈和CL-20/HMX/DMSO的三元相图;开展了温度对CL-20/HMX/丙酮和CL-20/HMX/DMSO三元相图的影响研究;基于溶液化学中的平衡理论,通过对以DMSO为溶剂时的溶解度数据拟合得到热力学参数溶度积常数(K_(sp))、络合常数(K_(11)和K_(21))和吉布斯自由能(ΔG^(0))。结果表明,HMX和CL-20在溶剂中的溶解度越大、溶解度差异越小,三元相图中的共晶区域越大、形状越对称;在20~35℃范围内,温度对CL-20/HMX/丙酮三元相图的形状和各区域大小影响较小,而对CL-20/HMX/DMSO三元相图的影响较为明显;随着温度升高,溶度积常数K_(sp)增大,CL-20/HMX共晶在DMSO中的溶解度增大;ΔG^(0)均为负值,表明CL-20和HMX在DMSO中的共晶为自发过程;CL-20/HMX共晶在DMSO中的溶液络合模型为1∶1+2∶1。To further analyze the formation process of hexanitrohexaazaisowurtzitane(CL-20)/cyclotetramethylenetetranitramine(HMX)cocrystal explosives and its dissolution behavior in solution,the solubility of HMX and CL-20 in pure solvents,and HMX in CL-20 solution with different concentrations were determined by high performance liquid chromatography.The ternary phase diagrams of CL-20/HMX/acetone,CL-20/HMX/acetonitrile and CL-20/HMX/dimethyl sulfoxide(DMSO)at 20℃were built.The effect of temperature on the CL-20/HMX/acetone and CL-20/HMX/DMSO ternary phase diagram was investigated.Moreover,the thermodynamic parameters of the solubility product(K_(sp)),complexation constants(K_(11)and K_(21))and the reaction free energy(ΔG^(0))were obtained through fitting the solubility data based on the mathematical models of solution chemistry theory.The results show that if the solubilities of CL-20 and HMX are larger and their discrepency is less in a solvent,the cocrystal region is larger and its shape is more symmetrical in the ternary phase diagrams.Within the range of 20~35℃,temperature has little effect on the shape and size of each region of the CL-20/HMX/acetone ternary phase diagram,while its effect on the CL-20/HMX/DMSO ternary phase diagram is more significant.As the temperature increases,the solubility product constant K_(sp)increases,which means the solubility of CL-20/HMX cocrystal in DMSO increases.ΔG^(0)is negative,indicating that cocrystal of CL-20 and HMX in DMSO is a spontaneous process.The solution complexation model in DMSO is 1∶1+1∶2.

关 键 词：CL-20 HMX 共晶炸药 溶解度 三元相图 热力学参数 

分 类 号：V512[航空宇航科学与技术—航空宇航推进理论与工程]