In this paper, the nitration characteristic of alcohols with mixed acid for the synthesis of energetic mate-rials in a stainless steel microreactor was investigated experimentally. The nitration of iso-octanol with HN...In this paper, the nitration characteristic of alcohols with mixed acid for the synthesis of energetic mate-rials in a stainless steel microreactor was investigated experimentally. The nitration of iso-octanol with HNO3-H2SO4 mixed acid was chosen as a typical model reaction which involved fast and strong exothermic liquid-liquid heterogeneous reaction process. The influences of mixed acid composition, flow rate, organic/aqueous flow ratio and reaction temperature have been investigated. The results indicated that the reaction could be con-ducted safely and stably in the microreactor at 25-40°C, which are enhanced compared to 15°C or below for safe operating conditions in the conventional reactors. Moreover, the 98.2% conversion of iso-octanol could be obtained and no by-products were detected in all cases.展开更多
以甲氧基甲酰肼与叠氮氰为原料,经成环、硝解、酸化、中和等反应合成高能材料1,5-二硝胺基四唑(DNAT)及其含能离子盐——钾盐(DKDNAT)、铵盐(DADNAT)、肼盐(DHDNAT)、羟胺盐(DHADNAT),采用红外光谱、1 H NMR、13 C NMR及元素分析对DNAT...以甲氧基甲酰肼与叠氮氰为原料,经成环、硝解、酸化、中和等反应合成高能材料1,5-二硝胺基四唑(DNAT)及其含能离子盐——钾盐(DKDNAT)、铵盐(DADNAT)、肼盐(DHDNAT)、羟胺盐(DHADNAT),采用红外光谱、1 H NMR、13 C NMR及元素分析对DNAT及其含能离子盐的结构进行了表征;优化了关键中间体1-甲氧基甲酰基-1,5-二氨基四唑(MCDAT)的合成工艺;探讨了一锅法合成MCDAT的反应机理;采用DSC方法对DNAT及其钾盐、铵盐、肼盐和羟胺盐的热性能进行了分析;对DNAT-CMDB、DHDNAT-CMDB、DHADNATCMDB推进剂的能量特性进行了理论研究。结果表明,叠氮氰与甲氧基甲酰肼的最佳摩尔比为1.2∶1.0,反应温度为25℃,MCDAT的收率由文献中的37.3%提高到79.3%;DNAT及其4种含能离子盐(钾盐、铵盐、肼盐和羟胺盐)的热分解峰温依次为94.1、259.1、192.1、142.8、146.7°C;3种推进剂的理论比冲分别为2 539.1、2 489.9、2 532.6N·s/kg,特征速度为1 571.6、1 570.1、1 580.6m/s。展开更多
基金Supported by the National Natural Science Foundation of China (20490208)the National High Technology Research and Development Program of China (2007AA030206)the Open Fund of State Key Laboratory of Explosion Science and Technology,BIT (KFJJ06-1)
文摘In this paper, the nitration characteristic of alcohols with mixed acid for the synthesis of energetic mate-rials in a stainless steel microreactor was investigated experimentally. The nitration of iso-octanol with HNO3-H2SO4 mixed acid was chosen as a typical model reaction which involved fast and strong exothermic liquid-liquid heterogeneous reaction process. The influences of mixed acid composition, flow rate, organic/aqueous flow ratio and reaction temperature have been investigated. The results indicated that the reaction could be con-ducted safely and stably in the microreactor at 25-40°C, which are enhanced compared to 15°C or below for safe operating conditions in the conventional reactors. Moreover, the 98.2% conversion of iso-octanol could be obtained and no by-products were detected in all cases.
