甲胺盐酸盐/发烟硝酸体系中DPT硝解?亚硝解反应制备MNX
|
摘要
用CH_3NH_2·HCl代替NH4NO3作为3,7-二硝基-1,3,5,7-四氮杂双环[3.3.1]壬烷(DPT)与发烟硝酸反应的添加剂,考察了CH_3NH_2·HCl对生成1-亚硝基-3,5,7-三硝基-1,3,5,7-四氮杂环辛烷(MNX)的影响。研究了CH_3NH_2·HCl促进DPT与发烟硝酸反应制备MNX的工艺,考察了发烟硝酸和CH_3NH_2·HCl的加入量、反应时间和反应温度对反应的影响。结果表明,通过正交实验确定的最佳反应条件为:n(DPT):n(CH_3NH_2·HCl)=1:2.5,反应时间10 min,反应温度-25℃。在最优反应条件下MNX的收率为78.5%。本方法避免使用NaNO_2溶液和N_2O_4作为亚硝基来源,简化了MNX的制备工艺,且反应废液容易处理,硝酸回收率为75%。CH_3NH_2·HCl对DPT与发烟硝酸反应的促进作用比NH_4NO_3的显著,提出了CH_3NH_2·HCl(或NH_4NO_3)分解成CH_3NH_3(或NH_3)作为Lewis碱催化剂促进DPT与发烟硝酸反应的可能机理,其中涉及到硝酸通过氧化还原反应生成亚硝酸作为亚硝基来源的过程。
CH_3 NH_2·HCl was used to replace NH_4 NO_3 as an additive in the reaction of 3,7-dinitro-1,3, 5, 7-tetraazabicyclo[3.3.1] nonane( DPT) in fuming nitric acid, and the effect of CH_3 NH_2·HCl on the formation of 1-nitroso-3,5,7-trinitro-1,3,5,7-tetraazacyclooctane(MNX) was investigated. The process of preparing MNX by CH_3 NH_2·HCl promoting the reaction of DPT with fuming nitric acid was studied. The effects of loading amounts of fuming nitric acid and CH_3 NH_2·HCl, reaction temperature and reaction time on the reaction were investigated. Results show that the optimum reaction conditions determined by orthogonal experiments are : n( DPT) : n(CH_3 NH_2·HCl) = 1 : 2.5, reaction time 10 min and reaction temperature-25℃. Under the optimum reaction conditions, the yield of MNX is 78.5%. This method avoids using NaNO_2 solution and N_2 O_4 as nitroso resource and simplifies the preparation process of MNX. The waste liquid is easy to be treated. The recovery of nitric acid is 75%.CH_3 NH_2·HCl can promote the reaction of DPT with fuming nitric acid more significantly than NH_4 NO_3. A possible mechanism of promoting the reaction of DPT and fuming nitric acid via decomposing CH_3 NH_2·HCl(or NH_4 NO_3)into CH_3 NH_2(or NH_3) as a Lewis base catalyst is proposed, which involves the process of nitrous acid formation from nitric acid through a redox reaction as nitroso resource.
CH_3 NH_2·HCl was used to replace NH_4 NO_3 as an additive in the reaction of 3,7-dinitro-1,3, 5, 7-tetraazabicyclo[3.3.1] nonane( DPT) in fuming nitric acid, and the effect of CH_3 NH_2·HCl on the formation of 1-nitroso-3,5,7-trinitro-1,3,5,7-tetraazacyclooctane(MNX) was investigated. The process of preparing MNX by CH_3 NH_2·HCl promoting the reaction of DPT with fuming nitric acid was studied. The effects of loading amounts of fuming nitric acid and CH_3 NH_2·HCl, reaction temperature and reaction time on the reaction were investigated. Results show that the optimum reaction conditions determined by orthogonal experiments are : n( DPT) : n(CH_3 NH_2·HCl) = 1 : 2.5, reaction time 10 min and reaction temperature-25℃. Under the optimum reaction conditions, the yield of MNX is 78.5%. This method avoids using NaNO_2 solution and N_2 O_4 as nitroso resource and simplifies the preparation process of MNX. The waste liquid is easy to be treated. The recovery of nitric acid is 75%.CH_3 NH_2·HCl can promote the reaction of DPT with fuming nitric acid more significantly than NH_4 NO_3. A possible mechanism of promoting the reaction of DPT and fuming nitric acid via decomposing CH_3 NH_2·HCl(or NH_4 NO_3)into CH_3 NH_2(or NH_3) as a Lewis base catalyst is proposed, which involves the process of nitrous acid formation from nitric acid through a redox reaction as nitroso resource.
引文
[1]于娜娜,王笃政.HMX的合成工艺研究进展[J].化工中间体,2011,8(3):22-26.YU Na-na,WANG Du-zheng.Review on the technology of synthesis of HMX[J].Chemical Intermediate,2011,8(3):22-26.
[2]Sun S,Zhang H,Liu Y.Transitions from separately crystal-lized CL-20 and HMX to CL-20/HMX cocrystal based on sol-vent media[J].Crystal Growth&Design,2018,18(1):77-84.
[3]Radhakrishnan S,Talawar M B,Venugopalan S.Synthesis,characterization and thermolysis studies on 3,7-dinitro-1,3,5,7-tetraazabicyclo[3,3,1]nonane(DPT):a key precursor in the synthesis of most powerful benchmark energetic materials(RDX/HMX)of today[J].Journal of Hazardous Materials,2008,152(3):1317-1324.
[4]宋红燕,王鹏,覃光明,等.一锅法合成二硝基五亚甲基四胺反应机理的研究[J].有机化学,2010,30(3):414-418.SONG Hong-yan,WANG Peng,QIN Guang-ming,et al.Re-action mechanism of one-pot synthesis of dinitro pentameth-ylene tetramine[J].Chinese of Journal Organic Chemistry,2010,30(3):414-418.
[5]He Z,Luo J,Lu C.Synthesis of HMX via nitrolysis of DPT cat-alyzed by acidic ionic liquids[J].Central European Journal of Energetic Materials,2011,8(2):83-91.
[6]陈里,陈浙闽,陈新虎.在硝酸一硝酸盐体系中DPT硝解反应的探索[J].火炸药,1986,3(3):1-5.CHEN Li,CHEN Zhe-min,CHEN Xin-hu.The explore of ni-trolysis of DPT by nitrate and nitric acid system[J].Chinese Journal of Explosives&Propellants,1986,3(3):1-5.
[7]李全良,陈军,王建龙.DPT制备HMX工艺研究[J].含能材料,2007,15(5):509-510.LI Quan-liang,CHEN Jun,WANG Jian-long.Synthesis craft of HMX from 1,5-methylene-3,7-dintrio-1,3,5,7-tetraazacy-clooctane[J].Chinese Journal of Energeic Materials(Hanneng Cailiao),2007,15(5):509-510.
[8]黄晓川,徐志斌,孟子晖,等.硝酸-硝酸铵体系中DPT硝解制备HMX工艺研究[J].应用化工,2013,42(2):299-303.HUANG Xiao-chuan,XU zhi-bin,MENG zi-hui,et al.Syn-thesis of HMX by nitrolysis of DPT in HNO3-NH4NO3[J].Applied Chemical Industry,2013,42(2):299-303.
[9]He Z Y,Luo J,Lu C X.Preparation of HMX by catalytic nitrol-ysis of DPT in AIL-N2O5-HNO3system[J].Bull Korean Chem Soc.2011,32(8):2677-2682.
[10]Zhi H Z,Luo J,Feng G A.An efficient method to synthesize HMX by nitrolysis of DPT with N2O5and a novel ionic liquid[J].Chinese Chemical Letters,2009,20(4):379-382.
[11]何志勇,罗军,吕春绪,等.N2O5硝解DPT制备HMX[J].火炸药学报,2010,33(2):1-4.HE Zhi-yong,LUO Jun,LüChun-xu,et al.Synthesis of HMXfrom DPT by green nitrolysis with dinitrogen pentoxide[J].Chinese Journal of Explosives&Propellants,2010,33(2):1-4.
[12]Bachmann W E,Jenner E L.1-Acetoxymethyl-3,5,7-trinitro-1,3,5,7-tetrazacyclo?ctane and its reactions.significance in the nitrolysis of hexamethylenetetramine and related compounds[J].Journal of American Chemical Society,1951,73(6):2773-2775.
[13]Mckay A F,Richmond H H,Wright G F.Nitrolysis of hexa-methylenetetramine;nitrolysis of 1,5-endomethylene-3,7-di-nitro-1,3,5,7-tetrazacyclo?ctane[J].Canadian Journal Research.1949,27(5):462-468.
[14]何志勇,罗军,吕春绪,等.3,7-二硝基-1,3,5,7-四氮杂双环[3.3.1]壬烷的硝解副产物及硝解机理[J].含能材料,2012,20(1):5-8.HE Zhi-yong,LUO Jun,LüChun-xu,et al.Mechanism and by-products of nitrolysis 3,7-dinitro-1,3,5,7-tetraazabicyclo[3,3,1]nonane[J].Chinese Journal of Energeic Materials(Hanneng Cailiao),2012,20(1):5-8.
[15]Liu W J,Xu Z B,Cui K J,et al.The nitrolysis mechanism of 3,7-dinitro-1,3,5,7-tetraazabicyclo[3,3,1]nonane.Propellants Explosives Pyrotechnics,2015,40(5):645-651.
[16]Zhang Y,Zou P,Luo J.A groundbreaking stepwise protocol to prepare HMX from DPT:new mechanism hypothesis and cor-responding process study[J].Propellants,Explosives,Pyrotechnics,2017,42(10):1208-1213.
[17]HUANG Xiao-chuan,Yu Tao,GE Zhong-xue,et al.Influence of ammonium ion of 3,7-dinitro-1,3,5,7-tetraazabicyclo[3.3.1]nonane(DPT)[J].Chinese Journal of Energeic Materials(Hanneng Cailiao),2015,23(11):1151-1154.
[18]张宇,徐子帅,罗军,等.DPT与红烟硝酸反应制备MNX[J].含能材料,2018,26(5):398-403.ZHANG Yu,XU Zhi-shuai,LUO Jun,et al.Synthesis of MNXfrom DPT in nitric acid[J].Chinese Journal of Energeic Materials(Hanneng Cailiao),2018,26(5):398-403.
[19]Farminer A R,Webb G A.NMR studies on some N-nitramines and N-nitrosamines[J].Tetrahedron,1975,31(13):1521-1526.
[20]Zhang Y,Zou P,Han Y B,et al.A combined experimental and DFT mechanistic study for the unexpected nitrolysis of N-hydroxytmethyldialkyiamines in fuming nitric acid[J].RSCAdvances,2018,8(34):19310-19316.
[21]苏秋宁,唐辉,刘志达.重氮化反应及其应用[J].精细化工中间体,2012(3):13-16.SU Qiu-ning,TANG Hui,LIU Zhi-da.The synthesis and appli-cation of diazonium[J].Fine Chemical Intermediates,2012(3):13-16.
[22]Butler R N.Diazotization of heterocyclic primary amines[J].Chemical Reviews,1975,75(2):241-257.
[23]周恩泽,王志广.一甲胺硝酸盐原料路线的探讨[J].辽宁化工,1994(2):51-52.ZHOU En-ze,WANG Zhi-guang.A discussion for the Synthe-sis of monomethylamine nitrate[J].Liaoning Chemical Industry,1994(2):51-52.
[24]He C F,Wang X,Sun Y Q,et al.Theoretical Study of the Gas-eous Hydrolysis of NO2in the Presence of Amines[J].The Journal of Physical Chemistry A,2016,121(1):226-237.
[2]Sun S,Zhang H,Liu Y.Transitions from separately crystal-lized CL-20 and HMX to CL-20/HMX cocrystal based on sol-vent media[J].Crystal Growth&Design,2018,18(1):77-84.
[3]Radhakrishnan S,Talawar M B,Venugopalan S.Synthesis,characterization and thermolysis studies on 3,7-dinitro-1,3,5,7-tetraazabicyclo[3,3,1]nonane(DPT):a key precursor in the synthesis of most powerful benchmark energetic materials(RDX/HMX)of today[J].Journal of Hazardous Materials,2008,152(3):1317-1324.
[4]宋红燕,王鹏,覃光明,等.一锅法合成二硝基五亚甲基四胺反应机理的研究[J].有机化学,2010,30(3):414-418.SONG Hong-yan,WANG Peng,QIN Guang-ming,et al.Re-action mechanism of one-pot synthesis of dinitro pentameth-ylene tetramine[J].Chinese of Journal Organic Chemistry,2010,30(3):414-418.
[5]He Z,Luo J,Lu C.Synthesis of HMX via nitrolysis of DPT cat-alyzed by acidic ionic liquids[J].Central European Journal of Energetic Materials,2011,8(2):83-91.
[6]陈里,陈浙闽,陈新虎.在硝酸一硝酸盐体系中DPT硝解反应的探索[J].火炸药,1986,3(3):1-5.CHEN Li,CHEN Zhe-min,CHEN Xin-hu.The explore of ni-trolysis of DPT by nitrate and nitric acid system[J].Chinese Journal of Explosives&Propellants,1986,3(3):1-5.
[7]李全良,陈军,王建龙.DPT制备HMX工艺研究[J].含能材料,2007,15(5):509-510.LI Quan-liang,CHEN Jun,WANG Jian-long.Synthesis craft of HMX from 1,5-methylene-3,7-dintrio-1,3,5,7-tetraazacy-clooctane[J].Chinese Journal of Energeic Materials(Hanneng Cailiao),2007,15(5):509-510.
[8]黄晓川,徐志斌,孟子晖,等.硝酸-硝酸铵体系中DPT硝解制备HMX工艺研究[J].应用化工,2013,42(2):299-303.HUANG Xiao-chuan,XU zhi-bin,MENG zi-hui,et al.Syn-thesis of HMX by nitrolysis of DPT in HNO3-NH4NO3[J].Applied Chemical Industry,2013,42(2):299-303.
[9]He Z Y,Luo J,Lu C X.Preparation of HMX by catalytic nitrol-ysis of DPT in AIL-N2O5-HNO3system[J].Bull Korean Chem Soc.2011,32(8):2677-2682.
[10]Zhi H Z,Luo J,Feng G A.An efficient method to synthesize HMX by nitrolysis of DPT with N2O5and a novel ionic liquid[J].Chinese Chemical Letters,2009,20(4):379-382.
[11]何志勇,罗军,吕春绪,等.N2O5硝解DPT制备HMX[J].火炸药学报,2010,33(2):1-4.HE Zhi-yong,LUO Jun,LüChun-xu,et al.Synthesis of HMXfrom DPT by green nitrolysis with dinitrogen pentoxide[J].Chinese Journal of Explosives&Propellants,2010,33(2):1-4.
[12]Bachmann W E,Jenner E L.1-Acetoxymethyl-3,5,7-trinitro-1,3,5,7-tetrazacyclo?ctane and its reactions.significance in the nitrolysis of hexamethylenetetramine and related compounds[J].Journal of American Chemical Society,1951,73(6):2773-2775.
[13]Mckay A F,Richmond H H,Wright G F.Nitrolysis of hexa-methylenetetramine;nitrolysis of 1,5-endomethylene-3,7-di-nitro-1,3,5,7-tetrazacyclo?ctane[J].Canadian Journal Research.1949,27(5):462-468.
[14]何志勇,罗军,吕春绪,等.3,7-二硝基-1,3,5,7-四氮杂双环[3.3.1]壬烷的硝解副产物及硝解机理[J].含能材料,2012,20(1):5-8.HE Zhi-yong,LUO Jun,LüChun-xu,et al.Mechanism and by-products of nitrolysis 3,7-dinitro-1,3,5,7-tetraazabicyclo[3,3,1]nonane[J].Chinese Journal of Energeic Materials(Hanneng Cailiao),2012,20(1):5-8.
[15]Liu W J,Xu Z B,Cui K J,et al.The nitrolysis mechanism of 3,7-dinitro-1,3,5,7-tetraazabicyclo[3,3,1]nonane.Propellants Explosives Pyrotechnics,2015,40(5):645-651.
[16]Zhang Y,Zou P,Luo J.A groundbreaking stepwise protocol to prepare HMX from DPT:new mechanism hypothesis and cor-responding process study[J].Propellants,Explosives,Pyrotechnics,2017,42(10):1208-1213.
[17]HUANG Xiao-chuan,Yu Tao,GE Zhong-xue,et al.Influence of ammonium ion of 3,7-dinitro-1,3,5,7-tetraazabicyclo[3.3.1]nonane(DPT)[J].Chinese Journal of Energeic Materials(Hanneng Cailiao),2015,23(11):1151-1154.
[18]张宇,徐子帅,罗军,等.DPT与红烟硝酸反应制备MNX[J].含能材料,2018,26(5):398-403.ZHANG Yu,XU Zhi-shuai,LUO Jun,et al.Synthesis of MNXfrom DPT in nitric acid[J].Chinese Journal of Energeic Materials(Hanneng Cailiao),2018,26(5):398-403.
[19]Farminer A R,Webb G A.NMR studies on some N-nitramines and N-nitrosamines[J].Tetrahedron,1975,31(13):1521-1526.
[20]Zhang Y,Zou P,Han Y B,et al.A combined experimental and DFT mechanistic study for the unexpected nitrolysis of N-hydroxytmethyldialkyiamines in fuming nitric acid[J].RSCAdvances,2018,8(34):19310-19316.
[21]苏秋宁,唐辉,刘志达.重氮化反应及其应用[J].精细化工中间体,2012(3):13-16.SU Qiu-ning,TANG Hui,LIU Zhi-da.The synthesis and appli-cation of diazonium[J].Fine Chemical Intermediates,2012(3):13-16.
[22]Butler R N.Diazotization of heterocyclic primary amines[J].Chemical Reviews,1975,75(2):241-257.
[23]周恩泽,王志广.一甲胺硝酸盐原料路线的探讨[J].辽宁化工,1994(2):51-52.ZHOU En-ze,WANG Zhi-guang.A discussion for the Synthe-sis of monomethylamine nitrate[J].Liaoning Chemical Industry,1994(2):51-52.
[24]He C F,Wang X,Sun Y Q,et al.Theoretical Study of the Gas-eous Hydrolysis of NO2in the Presence of Amines[J].The Journal of Physical Chemistry A,2016,121(1):226-237.