五唑金属盐分离纯化方法  

Separation and Purification of Metal Pentazolates

作　　者：龙婷 张思宇 刘天林 黄明[2] 李金勇 杨海君[1] LONG Ting;ZHANG Si-yu;LIU Tian-lin;HUANG Ming;LI Jin-yong;YANG Hai-jun(School of materials and chemistry,Southwest University of Science and Technology,Mianyang 621010,China;Institute of Chemical Materials,CAEP,Mianyang 621999,China)

机构地区：[1]西南科技大学材料与化学学院,四川绵阳621010 [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》2022年第9期966-970,共5页Chinese Journal of Energetic Materials

基　　金：国家自然科学基金资助(22075260)。

摘　　要：为解决五唑金属盐合成中分离纯化困难等问题,以芳基五唑C—N切断反应后处理所得五唑钠水溶液为研究对象,采用沉淀法对五唑金属盐进行了分离纯化研究。结果表明,五唑钠水溶液中含有大量有机酸盐,以及硝酸钠、氯化钠等无机盐杂质。与N5负离子相比,有机酸根更易与金属离子形成沉淀,从而影响五唑金属盐析出。将五唑钠水溶液调节为酸性,萃取除去有机酸盐后加入氯化钴,成功沉淀得到五唑钴金属盐。研究发现,pH值越低,有机酸盐的去除效率越高,五唑钴纯度越好。确定了五唑钴的适宜分离纯化条件:pH值为3,氯化钴与原料4‐氨基‐2,6‐二甲基苯酚(1)的摩尔比为0.26∶1。离子色谱表明,所得五唑钴经简单重结晶后纯度高达97.9%。在此基础之上,研究了沉淀法对其它五唑金属盐的适用性。结果表明,沉淀法亦适用于五唑铁、五唑亚铁和五唑铜等金属盐的分离纯化。Aiming at the difficulty in purification of metal pentazolates,the separation and purification of metal pentazolates were studied by precipitation method based on the aqueous solution of sodium pentazolate,which was obtained via C—N cleavage reaction of arylpentazole.Results show that the aqueous solution of sodium pentazolate contains a lot of organic acid salts,as well as inorganic salt impurities such as sodium nitrate and sodium chloride.Compared with N5 anions,the organic acid salts prefer to precipitate with metal ions in aqueous solution,thus affecting the precipitation of metal pentazolates.Cobalt pentazolate was precipitated from the aqueous solution of sodium pentazolate via acidification,removal of organic acid salts by extraction,and then addition of cobalt chloride.The lower the pH value is,the higher the removal efficiency of organic acid salts is and the higher the purity of cobalt pentazolate is.The optimized separation conditions of cobalt pentazolate are as follows:the pH value is 3,and the molar ratio of cobalt chloride to 4-amino-2,6-dimethylphenol(1)is 0.26∶1.The purity of cobalt pentazolate is up to 97.9%after simple recrystallization as shown by ion chromatography.The applicability of this precipitation method to other metal pentazolates was also studied.Results show that it is also suitable for the separation and purification of iron,ferrous and copper pentazolates.

关 键 词：含能材料 五唑金属盐 合成 沉淀法 工艺 分析表征 

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]