The Synthesis And Characterization Of2,2’,2",4,4’,4",6,6’,6"-nonanitroterphenyl

Nowdays, the heat-resistant explosive with good high heat resistance and detonation hasbeen one of the hot researches in the single-compound explosive synthesis field.2,2’,2",4,4’,4",6,6’,6"-nonanitroterphenyl（NONA） is an ideal heat-resistant explosive, as itsheat range of the solid is above300℃and its melting point is440～450℃. NONA wasdetermined to be the preferred aerospace medicine by NASA, for it can ensure100%detonated at high temperature and its has good crystalline and excellent performance ofdetonation.The aim of this study is to find the best process route of the synthesis of highpurity and high yield NONA, and offer theoretical foundation and experimental parametersfor industrial production.2,4,6-trinitrochlorobenzene was prepared by nitration of nitro-sulfuric acid starting with4-chloro-1-nitrobenzene by two steps. The optimal technological condition has beenestablished.In the first step, the quite good technique condition was:98%concentratedsulfuric acid:98%nitric acid:4-chloro-1-nitrobenzene=12.5ml:6.5ml:5g; nitrationtemperature:85℃;reaction time:2h.The production yield was about82%.In the second step，the quite good technique condition was:20%fuming sulfuric acid: nitrate ofpotash:2,4-dinitrochlorobenzene=16mL:7g:3g；nitration temperature:150℃,nitration time:5h.The production yield was about72%.2,4-dichloro-1,3,5-trinitrobenzene （DCTNB） was synthesized with2,4-dichloronitrobenzene as initial material by mixed acid method.The effect of material ratio,reaction time and reaction temperature on the yield of DCTNB was studied. An optionalproduction condition was: reaction temperature was150℃, reaction time was8h, and thenitration system was20%fuming sulphuric acid: fuming nitric acid=5:1（volume ratio）. Theproduction yield was64%.The purity of DCTNB was identified by thin-layer chromatographyand HPLC, and its structure was characterized by nuclear magnetic resonance spectroscopy.The single crystal of2,4-dichloro-1,3,5-trinitrobenzene was cultivated by solvent evaporationmethod starting with2,4-dichloro-1,3,5-trinitrobenzene. The single structure was determined by a four-circle X ray diffractometer. Crystalline structure showed that DCTNB belonged toorthorhombic system. Its crystallographic parameter wasa=0.59263（18）nm,b=1.4952（5）nm,c=1.0886（4）nm,α=β=γ=90o,V=0.9646（5）nm³,Z=4,Dc=1.942g/cm³,μ=0.696mm^-1,F（000）=560,R=0.0261,wR=0.0244S.NONA was synthesized with2,4,6-trinitro-chlorophenyl and2,4-dichloro-1,3,5-trinitrobenzene as raw materials,by intermolecular Ullmann-type coupling reaction,and thecopper-catalyzed Ullmann reaction was researched and overviewed. The reason of thegenerating of by-product in the reaction was discussed.The yield of NONA was about27-28%. Through characterization analysis, it was foundthat the main by-product contained HNBP and other high-polymer products. Obtained thetarget compound and separation steps were simplified by many different methods, whichincluded thin-layer chromatography combining column chromatography and differentproducts have different solubility in the same solvent.IR,¹HNMR and MS have been done to characterize the structure of NONA（product）,HNBP and DODECA （by-product）. At the same time, parts of the performance of targetproduct were tested and calculated.