N_2O_5/HNO_3硝解合成TEX工艺研究  

Optimization of Nitrolysis Synthesis Process of TEX by N_2O_5/HNO_3

作　　者：汤列金 吴珂 刘大斌[1] 钱华[1,3] 

机构地区：[1]南京理工大学化工学院,江苏南京210094 [2]常州出入境检验检疫局,江苏常州213003 [3]国家民用爆破器材质量监督检验中心,江苏南京210094

出　　处：《火炸药学报》2015年第6期11-15,31,共6页Chinese Journal of Explosives & Propellants

基　　金：国家自然科学基金(21406116);南京理工大学卓越计划"紫金之星";江苏省出入境检验检疫局科技计划项目(2014KJ59)

摘　　要：以N2O5/HNO3 为硝解剂、4种取代哌嗪为底物,制备了4,10-二硝基-2,6,8,12四氧杂-4,10-二氮杂四环[5.5.0.05.903.11]十二烷（TEX）,优化了目标产物的合成工艺;探讨了表面活性剂、酸性离子液体等催化剂对反应收率及纯度的影响.结果表明,以1,4-二甲酰基-2,3,5,6-四羟基哌嗪（DFTHP）作为硝解底物,加料温度为40℃,反应温度为75℃,反应时间为40min,加料比犿（DFTHP）∶m（N2O5）∶v（HNO3）为2g∶1g∶20mL 时,TEX 收率达45.6%,纯度达95.6%.当以十六烷基三甲基溴化铵（CTAB）、离子液体[Et3N（CH2）4SO3H][HSO4]和CF3SO3H/树脂（质量比为1∶9）为催化剂时,TEX 收率可进一步提高3%～14%.The 4,10-dinitro-2,6,8,1 2-tetraoxa-4,10-diazaisowutrzitane(TEX)was prepared using N2O5/HNO3 as nitrating agent and four different substituted piperazines as substrates,and the synthetic process of the target product was optimized.The effects of surfactants,acidic ionic liquids and other catalysts on the yield and purity of TEX were discussed.The results show that 1,4-diformyl-2,3,5,6-tetrahydroxypiperazine(DFTHP)is the best substrate and the optimum conditions are:feed temperature of 40℃,reaction temperature of 75℃,reaction time of40 min,and charging ratio of m(DFTHP)∶m(N2O5)∶V(HNO3)of 2g∶1g∶20mL,with a TEX yield of 45.6%and purity of 95.6%.Using hexadecyl trimethyl ammonium bromide(CTAB),[Et3N(CH2)4SO3H][HSO4]and CF3SO3H/resin with the mass ratio of 1∶9as catalysts,the yield of TEX can be further increased by 3%-14%.

关 键 词：有机化学 TEX 五氧化二氮 硝解 表面活性剂 酸性离子液体 哌嗪 

分 类 号：TJ55[兵器科学与技术—军事化学与烟火技术] TQ25[化学工程—有机化工]