N_2O_5/HNO_3/有机溶剂混合体系硝解DPT制备HMX  

Preparation of HMX by Nitrolysis of DPT in N_2O_5/HNO_3/Organic Solvent Mixed Systems

作　　者：胡衍甜 吕早生[1] 孙昱[1] 吕春绪[2] 

机构地区：[1]武汉科技大学化学工程与技术学院,湖北武汉430081 [2]南京理工大学化工学院,江苏南京210094

出　　处：《火炸药学报》2016年第2期50-53,58,共5页Chinese Journal of Explosives & Propellants

摘　　要：为了提高以N_2O_5为硝化剂的硝化体系硝解3,7-二硝基-1,3,5,7-四氮杂双环[3,3,1]壬烷(DPT)制备HMX的收率,考察了在N_2O_5/HNO_3/有机溶剂混合体系中,乙酸酐、乙腈、硝基甲烷、二氯甲烷4种有机溶剂与HNO_3在不同体积比下对DPT的硝解,测定了体系的H+浓度和N_2O_5的电导率,并分析了其对HMX收率的影响。结果表明,与4种N_2O_5/有机溶剂体系相比,N_2O_5/HNO_3/有机溶剂混合体系中产品收率明显提高;体系的酸度和硝化能力是影响HMX收率的两个重要因素,低酸度且硝化能力介于乙酰硝酸酯和NO2+之间时,有利于HMX生成;N_2O_5/HNO_3/乙酸酐混合体系为最适宜的硝解体系,当HNO_3与乙酸酐的体积比为3∶2时制备的HMX收率最高,为87.9%。In order to improve the yield of HMX prepared by nitrolysis of 3,7-dinitro-1,3,5,7-tetrazabicyelo[3,3,1]nonan(DPT)in the nitration system with N_2O_5 as nitrating agent,the nitrolysis of DPT in different volume ratio of four solvents(CH_3COOOCCH3,CH_3 CN,CH_3NO_2,CH_2C_l2)and HNO_3 was investigated in N_2O_5/HNO_3/organic solvent mixed systems.The concentration of H+of the system and electrical conductivity of N_2O_5 were measured and the effect on the yield of HMX was analyzed.Results show that compared with single solvent system,the yield of the product in N_2O_5/HNO_3/organic solvent mixed systems has been significantly improved.Acidity and nitrification ability of the mixed systems are the two important factors affecting the yield of HMX;low acidity and nitrification ability between acetyl nitrate and NO2+are beneficial to the formation of HMX.The N_2O_5/HNO_3/acetic anhydride system is the most suitable nitration system.When the volume ratio of HNO_3 and acetic anhydride is 3∶2,the highest yield of HMX prepared in N_2O_5/HNO_3/acetic anhydride system is 87.9%.

关 键 词：N2O5/HNO3/有机溶剂 硝解 酸度 硝化能力 3 7-二硝基-1 3 5 7-四氮杂双环[3 3 1]壬烷 DPT HMX 

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]