高纯 3,5⁃二氨基⁃2,4,6⁃三硝基氯苯的合成  

Synthesis of High Purity 3,5⁃Diamino⁃2,4,6⁃trinitrochlorobenzene

作　　者：罗郑航 王嘉璇 王雨晴 王鑫雨 张笑天 张理 张勇[2] 黄明[2] 杨海君[1] LUO Zheng-hang;WANG Jia-xuan;WANG Yu-qing;WANG Xin-yu;ZHANG Xiao-tian;ZHANG Li;ZHANG Yong;HUANG Ming;YANG Hai-jun(School of Materials and Chemistry,Southwest University of Science and Technology,Mianyang 621010,China;Institute of Chemical Materials,China Academy of Engineering Physics,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12期1191-1196,共6页Chinese Journal of Energetic Materials

基　　金：国家自然科学基金面上项目(22075260);四川省自然科学基金面上项目(2022NSFSC0288);装备部基础科研项目(192ZW22002)。

摘　　要：为了合成高纯3,5‑二氨基‑2,4,6‑三硝基氯苯(DATNCB),分别以1,3,5‑三氯‑2,4,6‑三硝基苯(TCTNB)或苦味酸(2)为原料,对DATNCB的合成进行了路径筛选及工艺优化研究。采用红外光谱、核磁共振、质谱分析对产物进行了结构表征;通过差示扫描量热仪和热失重分析仪研究了DATNCB的热分解及热失重历程;采用高效液相色谱对DATNCB进行了纯度分析。结果表明:以苦味酸为原料,经间接芳香亲核取代(VNS)氨基化再氯代是大量合成高纯DATNCB的适宜路线,总收率为39.2%;当VNS氨基化温度为90℃,后处理pH值为3时,3,5‑二氨基‑2,4,6‑三硝基苯酚(3)的收率最高为74.8%;以三氯氧磷/N,N‑二甲基苯胺为氯代试剂,反应温度为80℃,反应时间为10 h时,DATNCB的收率最高为52.4%;DATNCB的熔融温度为224.0℃,在179.7~270.9℃范围内存在1个失重阶段,失重率为91.6%,峰值分解温度为256.1℃;未经进一步纯化时DATNCB的纯度即达到97.09%,经乙酸乙酯/石油醚重结晶纯化后纯度达到99.8%。In order to synthesize high‑purity 3,5‑diamino‑2,4,6‑trinitrochlorobenzene(DATNCB),the synthesis route screening and process optimization of DATNCB were studied with 1,3,5‑trichloro‑2,4,6‑trinitrobenzene(TCTNB)or picric acid(2)as raw materials,respectively.The structure of the product was characterized by IR,NMR and MS;the thermal behavior of DATNCB was studied by DSC‑TG;the purity of DATNCB was analyzed by HPLC.The results show that:the best synthetic route of DATNCB is starting from picric acid,then by via VNS amination followed by chlorination.The total yield is 39.2%.The high‑est yield of 3,5‑diamino‑2,4,6‑trinitrophenol(3)was 74.8%when VNS amination temperature was 90℃and post‑treatment pH value was 3;the highest yield of DATNCB was 52.4%when phosphorus oxychloride/N,N‑dimethylaniline was used as the chlorination reagent,the reaction temperature was 80℃and the reaction time was 10 h.The melting point of DATNCB is 224.0℃.There is only one weight loss stage in the range of 179.7-270.9℃and the weight loss rate is 91.6%;the peak decom‑position temperature is 256.1℃.The purity of DATNCB reach 97.09%without further purification,and up to 99.8%after recrys‑tallization with ethyl acetate/petroleum.

关 键 词：内标物 高纯DATNCB VNS氨基化 氯代反应 热性能 

分 类 号：TJ55[兵器科学与技术—军事化学与烟火技术] O64[理学—物理化学]