高能低感熔铸炸药液相载体3,3'-联(1,2,4-噁二唑)-5,5'-二甲硝酸酯的合成及性能
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摘要
以二氨基乙二肟与乙酰氧基乙酰氯为原料,经环化、水解、硝化合成了新型熔铸炸药液相载体3,3'-联(1,2,4-噁二唑)-5,5'-二甲硝酸酯(BODN),总收率为54%,并采用红外光谱、核磁共振、元素分析等进行了结构表征;优化了水解与硝化反应条件;基于分离、鉴定反应副产物的实验结果,探讨了BODN环化反应机理;利用DSC法研究了BODN与RDX、HMX、CL-20的相容性;采用EXPLO5软件预估了RDX、HMX、CL-20为固相的BODN基熔铸炸药的爆轰参数。结果表明,水解反应较优条件为:以碳酸钾为水解试剂在甲醇中回流,其中,3,3'-联(1,2,4-噁二唑)-5,5'-二甲醇乙酸酯和碳酸钾的摩尔比为10∶1,反应2h;硝化反应较优体系为98%发烟硝酸/醋酐体系,其中,98%发烟硝酸、醋酐体系及3,3'-联(1,2,4-噁二唑)-5,5'-二甲醇的摩尔比为10∶5∶1,反应10h; BODN分解峰温203.2℃,与RDX、HMX和CL-20均可良好相容; BODN/CL-20(质量比7∶3)理论爆速达8595m/s,较TNT/C L-20爆速提高约900m/s。
Using diaminogly oxime and 2-chloro-2-oxo ethyl acetate as rawmaterials, a melt-easting explosive, 3,3'-bi(1,2,4-oxadiazole)-5,5'-diylbis(methylene) dinitrate(BODN), was synthesized via coupling-dehydration cyclization, hydrolysis and nitration with an o verall yield of 54%, and its structure was characterized by IR, 1H NMR, 13 CNMR and elemental analysis. The reaction conditions of hydrolysis and nitrition were optimized. Based on the separation and identification of reaction by-product, the mechanism of BO DN coupling-dehydration cyclization reaction was discussed. The compatibilities of BODN with RDX, HMX and CL-20 were investigated by DSC method. The detonation parameters of BODN-based melt-casting explosives with RDX, HM X and C L-20 as solid phase were predicted by EXPLO5 software.The results showthat the preferred hydrolysis conditions are as follows : n([3,3'-bi(1,2,4-oxadiazole) ]-5,5'-diylbis(methylene)diacetate) : n(K_2CO_3) is 10 : 1 and the reacting time is 2 h with reflux in CH_3OH and K_2CO_3 as hydrolysis solvent. The preferred reaction conditions for nitrition are: under 98% fuming nitric acid/acetic anhydride system, the molar ratio of the 98% fuming nitric acid/acetic anhydride/[3,3'-bi(1,2,4-oxadiazole) ]-5,5'-diylbis(methy lene) is10 :5 :1,reaction time of 10 h. The decomposition peak temperature of BODN is 203.2℃ and it has good compatibility with RDX,HMX and CL-20. The theoretical detonation velocity of BODN/CL-20 with a mass ratio of 7 : 3 reaches to8595 m/s, 900 m/s higher than that of TNT/CL-20.
Using diaminogly oxime and 2-chloro-2-oxo ethyl acetate as rawmaterials, a melt-easting explosive, 3,3'-bi(1,2,4-oxadiazole)-5,5'-diylbis(methylene) dinitrate(BODN), was synthesized via coupling-dehydration cyclization, hydrolysis and nitration with an o verall yield of 54%, and its structure was characterized by IR, 1H NMR, 13 CNMR and elemental analysis. The reaction conditions of hydrolysis and nitrition were optimized. Based on the separation and identification of reaction by-product, the mechanism of BO DN coupling-dehydration cyclization reaction was discussed. The compatibilities of BODN with RDX, HMX and CL-20 were investigated by DSC method. The detonation parameters of BODN-based melt-casting explosives with RDX, HM X and C L-20 as solid phase were predicted by EXPLO5 software.The results showthat the preferred hydrolysis conditions are as follows : n([3,3'-bi(1,2,4-oxadiazole) ]-5,5'-diylbis(methylene)diacetate) : n(K_2CO_3) is 10 : 1 and the reacting time is 2 h with reflux in CH_3OH and K_2CO_3 as hydrolysis solvent. The preferred reaction conditions for nitrition are: under 98% fuming nitric acid/acetic anhydride system, the molar ratio of the 98% fuming nitric acid/acetic anhydride/[3,3'-bi(1,2,4-oxadiazole) ]-5,5'-diylbis(methy lene) is10 :5 :1,reaction time of 10 h. The decomposition peak temperature of BODN is 203.2℃ and it has good compatibility with RDX,HMX and CL-20. The theoretical detonation velocity of BODN/CL-20 with a mass ratio of 7 : 3 reaches to8595 m/s, 900 m/s higher than that of TNT/CL-20.
引文
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[2]王亲会.熔铸混合炸药用载体炸药评述[J].火炸药学报,2011,34(5):25-28.WAN G Q in-hui.O verviewof carrier explosive for meltcast composite explosive[J].C hinese Journal of Explosives&Propellants(Huoz hayao Xuebao),2011,34(5):25-28.
[3]Levine B S,Furedi E M,Gordon D E,et al.Toxic interactions of the munitions compounds TNTand RDX in F344 rats[J].Toxicological Sciences,1990,15:373-380.
[4]吴耀国,赵大为,赵晨辉,等.TNT的O3/H2O2降解规律[J].火炸药学报,2004,27(3):42-45.WU Yao-guo,Z HAO D a-wei,Z HAO C hen-hui,et al.D egradation of TN Tby O3/H2O2[J].Chinese Journal of Explosives&Propellants(Huoz hayao Xuebao),2004,27(3):42-45.
[5]Johnson C E,Sabatini J J,Chavez E D,et al.Bis(1,2,4-oxadiazole)bis(methylene)dinitrate:a high-energy melt castable explosive and energetic propellant plasticizing ingredient[J].O rganic Process Research&Development,2018,22:736-740.
[6]Beach N R,Canfield V K Y.Compatibility of explosives with polymers,AD 721004[R].Springfield:N TIS,1971.
[7]严启龙,李笑江,廖林泉,等.四硝基并哌嗪(TNAD)与推进剂组分相容性的DSC法评估[J].含能材料,2008,16(3):309-314.YAN Q i-long,LI Xiao-jiang,LIAO Lin-quan,et al.C ompatibility of trans-1,4,5,8-tetranitro-1,4,5,8-tetraazadacalin(TN AD)with some propellant components evaluated by D SC method[J].C hinese Journal of Energetic Materials,2008,16(3):309-314.
[8]GJB7724-1997 502.1.DTA和DSC测试安定性和相容性[S].1997.
[9]薛琪,毕福强,张家荣,等.异呋咱含能化合物合成及性能研究进展[J].有机化学,DOI:10.6023/cjoc201811029.XU E Q i,BI Fu-qiang,Z HAN G Jia-rong,et al.Advances in the synthesis and properties of the isofurazan energetic compounds[J].C hinese Journal of O rganic C hemistry.DO I:10.6023/cjoc201811029.
[10]毕福强,葛忠学,孙序东,等.1,1'-二羟基-5,5'-联四唑二羟胺盐和CMDB推进剂组份的相容性[J].含能材料,2014,22(5):716-718.BI Fu-qiang,GE Z hong-xue,SU N Xu-dong,et al.C ompatibility of dihydroxylammonium 5,5'-bistetrazole-1,1'-diolate with components of C MD B propellant[J].C hinese Journal of Energetic Materials,2014,22(5):716-718.
[11]Svc'eska M.EXPLO5 V6.01[M].Croatia:Brodarski Institute,2012.
[12]何飘,杨俊清,李彤,等.含能材料量子化学计算方法综述[J].含能材料,2018,26(1):34-45.HE Piao,YAN G Jun-qing,LI Tong,et al.O verviewon the quantum chemical methods for energetic materials[J].Chinese Journal of Energetic Materials,2018,26(1):34-45.
[13]魏伦,王琼林,刘少武,等.高能量密度化合物CL-20、D N TF和AD N在高能发射药中的应用[J].火炸药学报,2009,32(1):17-20.WEI Lun,WAN G Q iong-lin,LIU Shao-wu,et al.Application of high energy density compounds C L-20,D N TFand AD Nin high energy propellant[J].C hinese Journal of Explosives&Propellants(Huoz hayao Xuebao),2009,32(1):17-20.
[14]Suc'eska M.Calculation of the detonation properties of C-H-N-O explosives[J].Propellants,Explosives,Pyrotechnics,1991,16:197-202.
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