二硝基乙腈钾盐的合成、热行为及晶体形貌
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摘要
以氰基乙酸乙酯为原料,通过亚硝化、硝化?水解反应,合成了二硝基乙腈钾盐,总收率为76.93%。其结构用红外光谱、核磁共振和元素分析表征。通过添加不同表面活性剂、改变降温速率和搅拌转速等手段,制备了不同形貌的二硝基乙腈钾盐样品。用DSC研究了不同晶体形貌的二硝基乙腈钾盐的热分解过程,并测试了其机械感度。结果表明,二硝基乙腈钾盐的晶体形态对样品的热分解过程影响不大。加入表面活性剂聚乙二醇(400)后得到的二硝基乙腈钾盐样品的感度最低(撞击感度为8%,摩擦感度为12%,H_(50)>129.5 cm)。
Potassium dinitroacetonitrile was synthesized via the reactions of nitrosation and nitration?hydrolysis using ethyl cyano?acetate as raw material with a total yield of 76.93%,and its structure was characterized by NMR,IR and elemental analysis. The samples of potassium dinitroacetonitrile with different crystal morphologies were prepared by adding the different surfactants,changing the cooling rate and stirring speed. The thermal decomposition process of potassium dinitroacetonitrile with different crystal morphologies was studied by DSC and their mechanical sensitivities were tested. Results show that the crystal morphology of potassium dinitroacetonitrile has little effect on the thermal decomposition process of the sample. The sensitivity of potassium dinitroacetonitrile sample obtained after the addition of surfactant polyethylene glycol(400)is the lowest(the impact sensitivity is 8%,the friction sensitivity is 12% and the characteristic drop heights of impact sensitivity H_(50) is >129.5 cm).
Potassium dinitroacetonitrile was synthesized via the reactions of nitrosation and nitration?hydrolysis using ethyl cyano?acetate as raw material with a total yield of 76.93%,and its structure was characterized by NMR,IR and elemental analysis. The samples of potassium dinitroacetonitrile with different crystal morphologies were prepared by adding the different surfactants,changing the cooling rate and stirring speed. The thermal decomposition process of potassium dinitroacetonitrile with different crystal morphologies was studied by DSC and their mechanical sensitivities were tested. Results show that the crystal morphology of potassium dinitroacetonitrile has little effect on the thermal decomposition process of the sample. The sensitivity of potassium dinitroacetonitrile sample obtained after the addition of surfactant polyethylene glycol(400)is the lowest(the impact sensitivity is 8%,the friction sensitivity is 12% and the characteristic drop heights of impact sensitivity H_(50) is >129.5 cm).
引文
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[15]杨利,任晓婷,张同来,等.超细HNS的形貌控制及性能[J].火炸药学报,2010,33(1):19-23.YANG Li,REN Xiao-ting,ZHANG Tong-lai,et al.Crystal morphology control and properties of ultrafine HNS[J].Chinese Journal of Explosives&Propellants,2010,33(1):19-23.
[16]李岗,陈健,王晶禹,等.HNS微晶形貌控制研究[J].山西化工,2009,29(2):7-10.LI Gang,CHEN Jian,WANG Jing-yu,et al.Study on the crystal morphology of ultrafine HNS[J].Shanxi Chemical Industry,2009,29(2):7-10.
[2]李玉祥.高燃速发射药及其燃烧性能研究[D].南京:南京理工大学,2015.LI Yu-xiang.Study on high burning rate gun propellant and its combustion performance[D].Nanjing:Nanjing university of science&technology,2013.
[3]Chaille J L,Walker R B.Solid nitrocellulose-nitroglycerin propellant with burning rate modifiers containing dinitrocetonitrile salts:US3450583[P],1969.
[4]Kettner M A,Klapotke T M.New energetic polynitrotetrazoles[J].Chemistry A European Journal,2015 21(9):3755-3765.
[5]Haiges R,Christe K O.5-(fluorodinitromethyl)-2h-tetrazole and its tetrazolates-preparation and characterization of new high energy compounds[J].Dalton Transactions,2015,44(22):10166-10176.
[6]Parker C O,Ala H.Dinitrocyanoacetates:US 2926484[P],1960.
[7]Parker C O,Ala H.Process for the preparation of dinitroacetonitrile and salts:US 3415867[P],1968.
[8]Parker C O,Emmons W D,Rolewicz H A,et al.Preparation and properties of dinitroacetonitrile and its salts[J].Tetrahedron,1962,17(1):79-87.
[9]尚雁,叶志虎,王友兵,等.HNS-Ⅳ的制备及粒径、形貌控制[J].含能材料,2011,19(3):299-304.SHANG Yan,YE Zhi-hu,WANG You-bing,et al.Preparation,particle size and crustal control of HNS-Ⅳ[J].Chinese Journal of Energetic Materials(Hanneng Cailiao),2011,19(3):299-304.
[10]周群,陈智群,王伯周,等.FOX-7晶体形貌对感度的影响[J].火炸药学报,2014,37(5):67-69.ZHOU Qun,CHEN Zhi-qun,WANG Bo-zhou,et al.Effect of morphology of fox-7 crystals on its sensitivity[J].Chinese Journal of Explosives&Propellants,2014,37(5):67-69.
[11]许诚,张敏,毕福强,等.重结晶工艺对1,1-二羟基-5,5-联四唑羟胺盐热性能和机械感度的影响[J].含能材料,2017,25(5):409-412.XU Cheng,ZHANG Min,BI Fu-qiang,et al.Influence of recrystallization process on the thermal properties and mechanical sensitivity of dihydroxylammonium 5,5'-bistetrazole-1,1'-diolate(HATO)(J).Chinese Journal of Energetic Materials(Hanneng Cailiao),2017,25(5):409-412.
[12]GJB 772A-1997炸药测试方法[S].北京:中国标准出版社.GJB 772A-1997 Explosive test method[S].Beijing:China Standard Press.
[13]徐容,李洪珍,黄明,等.球形化HMX制备及性能研究[J].含能材料,2018,18(5):505-509.XU Rong,LI Hong-zhen,HUANG Ming,et al.Preparation and properties of rounded HMX[J].Chinese Journal of Energetic Materials(Hanneng Cailiao),2018,18(5):505-509.
[14]任晓婷,杜涛,何金选,等.双(2,2,2-三硝基乙基)胺的晶体形貌预测及控制[J].含能材料,2015,23(8):737-740.REN Xiao-ting,DU Tao,HE Jin-xuan,et al.Prediction and control of crystal morphology of BTNA[J].Chinese Journal of Energetic Materials(Hanneng Cailiao),2015,23(8):737-740.
[15]杨利,任晓婷,张同来,等.超细HNS的形貌控制及性能[J].火炸药学报,2010,33(1):19-23.YANG Li,REN Xiao-ting,ZHANG Tong-lai,et al.Crystal morphology control and properties of ultrafine HNS[J].Chinese Journal of Explosives&Propellants,2010,33(1):19-23.
[16]李岗,陈健,王晶禹,等.HNS微晶形貌控制研究[J].山西化工,2009,29(2):7-10.LI Gang,CHEN Jian,WANG Jing-yu,et al.Study on the crystal morphology of ultrafine HNS[J].Shanxi Chemical Industry,2009,29(2):7-10.