摘要
采用微通道式反应技术,分别以1-甲基-2,4-二硝基咪唑(2,4-MDNI)与硝硫混酸硝化反应、2,4,5-三硝基咪唑钾盐(2,4,5-TNIK)与硫酸二甲酯(DMS)甲基化反应,合成了1-甲基-2,4,5-三硝基咪唑(MTNI);采用傅里叶变换红外光谱(FT-IR)、核磁共振光谱(NMR)、元素分析(EA)、熔点等表征了其结构。结果表明,采用微通道反应技术,基于2,4-MDNI硝化工艺的最优条件为:2,4-MDNI和发烟硝酸摩尔比为2∶3、发烟硝酸和20%发烟硫酸体积比为1∶2、在微通道反应器中停留时间为12min、反应器中反应液温度为75℃,得率和纯度分别为78.1%和99.2%。基于2,4,5-TNIK甲基化工艺的最优条件为:2,4,5-TNIK、DMS和K2CO3摩尔比为1∶2∶2、在微通道反应器中停留时间为20min、反应温度为70℃,得率和纯度分别为71.3%和99.4%。由此可得,微通道式反应工艺与常规釜式反应工艺相比,具有反应时间短、硝化试剂用量少、反应温度略有降低、得率略有提高的优点。
1-Methyl-2,4,5-trinitroimidazole(MTNI)was synthesized by nitration of 1-methyl-2,4-dinitroimidazole(2,4-MDNI)with nitric-sulfuric mixed acid,and methylation of potassium 2,4,5-trinitroimidazole(2,4,5-TNIK)with dimethyl sulfate(DMS)using micro-channel reaction technology,respectively.The structure was characterized by fourier transform infrared spectroscopy(FT-IR),nuclear magnetic resonance spectroscopy(NMR),elemental analysis(EA)and melting point testing.The results show that by using micro-channel reaction process,the optimal conditions based on nitration of 2,4-MDNI are as follows:the molar ratio of 2,4-MDNI and fuming nitric acid is 2∶3,the volume ratio of fuming nitric acid and fuming sulfuric acid is 1∶2,the reaction time is 12 min,the reaction temperature is 75℃,the yield and purity are 78.1%and 99.2%,respectively.The optimal conditions based on methylation of 2,4,5-TNIK are as follows:the molar ratio of 2,4,5-TNIK,DMS and K 2CO 3 is 1∶2∶2,the reaction time is 20 min,the reaction temperature is 70℃,the yield and purity are 71.3%and 99.4%,respectively.Therefore,compared with the conventional tank reactor process,the micro-channel reaction process has the advantages of shorter reaction time,lower dosage of nitration reagent,slightly lower reaction temperature and slightly higher yield.
作者
廉鹏豹
张源
谷玉龙
吴静静
赵芦奎
曹彩
王建龙
LIAN Peng-bao;ZHANG Yuan;GU Yu-long;WU Jing-jing;ZHAO Lu-kui;CAO Cai;WANG Jian-long(Shanxi North Xingan Chemical Industry Co.Ltd.,Taiyuan 030008,China;School of Chemistry and Chemical Engineering,North University of China,Taiyuan 030051,China)
出处
《火炸药学报》
EI
CAS
CSCD
北大核心
2024年第6期541-548,I0004,共9页
Chinese Journal of Explosives & Propellants
