1,4-二硝基咪唑的溶解性能、热性能和感度
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摘要
为得到1,4-二硝基咪唑(1,4-DNI)的理化性能,用重力法测定了1,4-DNI在4种不同溶剂(丙酮、乙酸乙酯、甲醇、乙醇)中的溶解度,用溶解度数据估算了1,4-DNI的标准溶解焓、标准溶解熵和标准吉布斯自由能,探究了1,4-DNI在不同溶剂中的结晶形貌;通过差示扫描量热法(DSC)和热重法(TG)研究了1,4-DNI的热性能,用Kissinger法计算了其表观活化能;测试了1,4-D N I的机械感度。结果表明,1,4-DNI在4种溶剂中的溶解度均随温度的升高而增加,其溶解是一个非自发的吸热过程,溶解度值由大到小的顺序为:丙酮>乙酸乙酯>甲醇>乙醇;用丙酮和乙酸乙酯作溶剂,采用冷却结晶法得到的晶体结晶品质优于甲醇和乙醇,结晶产率和纯度也较高;当升温速率为10K/min时,1,4-DNI的熔融温度为95.0℃,分解峰温为167.6℃,热重变化的温度范围为134.7～340.8℃,总失重率为94%,其表观活化能为119.26kJ/mol; 1,4-DNI实测撞击感度大于20J,摩擦感度为60N。
To obtain the physicochemical properties of 1,4-dinitroimidazole(1,4-DNI), the solubility of 1,4-DNI in four different solvents(acetone, ethyl acetate, methanol and ethanol) was determined by the gravimetric method, which was em ployed to estim ate the standard enthalpy of dissolutio n, standard entro py of dissolution, and standard Gibbs free energy of dissolution. The crystallization morphologies of 1,4-DNI in different so lvents were investigated. Therm al properties of1,4-DNI were studied by differential scanning calorimetry(DSC) and thermogravimetry(TG), and the apparent activation energy was calculated by Kissinger's method. The mechanical sensitivity of 1,4-DNI was also tested. The results showthat the so lubility of 1,4-DNI in fo ur solvents increases with the increase of temperature, and its disso lutio n is a non-spontaneous and endothermic process. The solubility of 1,4-DNI is ranked as acetone > ethyl acetate > methanol > ethanol. The quality, yield and purity of 1,4-DNI crystal obtained by cooling in acetone and ethyl acetate are higher than those in methanol and ethanol. W hen the heating rate is lOK/min, the melting temperature and decomposition peak temperature of 1,4-DNI are 95.0℃ and 167.6℃,respectively. The temperature change range of TG is 134.7-340.8℃ with the total mass loss rate of 94%, and the apparent activation energy is 119.26 kJ/mol. T he im pact sensitivity of 1,4-D NI determined experimentally is more than 20 J and its friction sensitivity is 60 N.
To obtain the physicochemical properties of 1,4-dinitroimidazole(1,4-DNI), the solubility of 1,4-DNI in four different solvents(acetone, ethyl acetate, methanol and ethanol) was determined by the gravimetric method, which was em ployed to estim ate the standard enthalpy of dissolutio n, standard entro py of dissolution, and standard Gibbs free energy of dissolution. The crystallization morphologies of 1,4-DNI in different so lvents were investigated. Therm al properties of1,4-DNI were studied by differential scanning calorimetry(DSC) and thermogravimetry(TG), and the apparent activation energy was calculated by Kissinger's method. The mechanical sensitivity of 1,4-DNI was also tested. The results showthat the so lubility of 1,4-DNI in fo ur solvents increases with the increase of temperature, and its disso lutio n is a non-spontaneous and endothermic process. The solubility of 1,4-DNI is ranked as acetone > ethyl acetate > methanol > ethanol. The quality, yield and purity of 1,4-DNI crystal obtained by cooling in acetone and ethyl acetate are higher than those in methanol and ethanol. W hen the heating rate is lOK/min, the melting temperature and decomposition peak temperature of 1,4-DNI are 95.0℃ and 167.6℃,respectively. The temperature change range of TG is 134.7-340.8℃ with the total mass loss rate of 94%, and the apparent activation energy is 119.26 kJ/mol. T he im pact sensitivity of 1,4-D NI determined experimentally is more than 20 J and its friction sensitivity is 60 N.
引文
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[28]王振宇.国外近年研制的新型不敏感单质炸药[J].含能材料,2003,11(4):227-230.WAN G Z hen-yu.D evelopment on some newinsensitive individual explosives abroad[J].C hinese Journal of Energetic Materials,2003,11(4):227-230.
[2]Sanner MA,Helal C J,Cooper C B,et al.Imidazole derivatives:U S,2002119963[P].2002.
[3]Li Q,Xing J H,Cheng H B,et al.Design,synthesis,antibacterial evaluation and docking study of novel 2-hydroxy-3-(nitroimidazolyl)-propyl-derived quinolone[J].C hemical Biology&Drug Design,2015,85(1):79-90.
[4]Qu Y Y,Chen Y,Chi Y,et al.Synthesis of 1-amino-2,4-D initroimidazole optimized by online infrared spectroscopy and its spectroscopy and its energetic properties[J].C hempluschem,2017,82(2):287-294.
[5]Song J H,Wang K,Liang L X,et al.High-energy-density materials based on 1-nitramino-2,4-dinitroimidazole[J].Rsc Advance,2013,3(27):10859-10866.
[6]Bernadette B T,Rafal J,David T,et al.ChemInform abstract:1-aryl-4-nitro-1H-imidazoles,a newpromising series for the treatment of human african trypanosomiasis[J].European Journal of Medicinal Chemistry,2011,46(5):1524-1535.
[7]Damavarapu R,Jayasuriya K,Vladimiroff T,et al.2,4-dinitroimidazole-a less sensitive explosive and propellant made by thermal rearrangement of molten 1,4-dinitro-imidazole:U S,5387297[P].1995.
[8]Jin R C,Soo G C,Kwang J K,et al.Insensitive munitions&engergetic materials technology symposium[C]∥A Candidate of NewInsensitive High Explosive MTN I.[S.l.]:C heminform,2000,39(23):393-400.
[9]曹端林,刘慧君,李永祥.1,4-二硝基咪唑的合成及其热分解[J].火炸药学报,2005,28(3):60-62.C AO D uan-lin,LIU Hui-jun,LI Yong-xiang.Synthesis and decomposition characteristics of 1,4-dinitroimidazole[J].Chinese Journal of Explosives&Propellants(Huozhayao Xuebao),2005,28(3):60-62.
[10]刘慧君,樊月琴,冯峰,等.1,4-DNI的绿色合成[J].山西大同大学学报(自然科学版),2011,27(2):37-38.LIU Hui-jun,FAN Yue-qin,FEN G Feng,et al.The green synthesis of 1,4-D N I[J].Journal of Shanxi Datong University(N atural Science Edition),2011,27(2):37-38.
[11]侯可辉.硝基咪唑类含能化合物的合成、表征和性能研究[D].南京:南京理工大学,2014.HO U Ke-hui.Synthesis,characterization and properties of nitroimidazole energetic compounds[D].N anjing:N anjing U niversity of Science and Technology,2014.
[12]Lv P H,Wang H Y,Tong Y,et al.Measurement and correlation of the solubility ofε-C L-20 in 12 organic solvents at temperatures ranging from 278.15 to 318.15 K[J].Journal of Chemical&Engineering Data,2017,62(3):961-966.
[13]Gurunadham M,Kushalava R Y,Samsher S,et al.Synthesis of newgeneration triazolyl and isoxazolyl containing6-nitro-2,3-dihydroimidazooxazoles as anti-TB agents:in vitro,structure-activity relationship,pharmacokinetics and in vivo evaluation[J].O rganic&Biomolecular C hemistry,2015,13(12):3610-3624.
[14]马茹燕,陈玥.1,4-二硝基咪唑的制备工艺研究[J].太原师范学院学报(自然科学版),2013,12(3):118-120.MA R u-yan,C HEN Yue.1,4-D initroimidazole preparation research[J].Journal of Taiyuan N ormal University(Natural Science Edition),2013,12(3):118-120.
[15]Schr9der B,Santos L MN B F,Marrucho I M,et al.Prediction of aqueous solubilities of solid carboxylic acids with C O SMO-R S[J].Fluid Phase Equilibria,2010,289(2):140-147.
[16]Gabas N,Laguerie C.Dispersion of growth rates of d-xylose crystals in aqueous solutions-influence of the presence of ethanol as a co-solvent and of d-mannose as a co-solute[J].Chemical Engineering Science,1991,46(5):1411-1418.
[17]Zhou L,Zhang P P,Yang G D,et al.Solubility of chrysin in ethanol and water mixtures[J].Journal of C hemical&Engineering Data,2014,59(7):2215-2220.
[18]Wang N,Fu Q,Yang G D,et al.Determination of the solubility,dissolution enthalpy and entropy of icariin in water,ethanol,and methanol[J].Fluid Phase Equilibria,2012,324(324):41-43.
[19]Lan G C,Wang J L,Chen L Z,et al.Determination and correlation of the solubility of 3,4-bis(3-nitrofurazan-4-yl)furoxan(D N TF)in different solvents[J].The Journal of C hemical Thermodynamics,2015,89(5):264-269.
[20]Ksiazczak A,Moorthi K,Nagata I,et al.Solid-solid transition and solubility of even n-alkanes[J].Fluid Phase Equilibria,1994,95(389):15-29.
[21]Zhang F,Tang Y C,Wang L,et al.Solubility measurement and correlation for 2-naphthaldehyde in pure organic solvents and methanol+ethanol mixtures[J].Journal of C hemical&Engineering Data,2015,60(8):2502-2509.
[22]Perlovich G L,Kurkov S V,Bauer-Brandl A,et al.Thermodynamics of solutionsⅡ.Flurbiprofen and diflunisal as models for studying solvation of drug substances[J].European Journal of Pharmaceutical Sciences,2003,57(2):423-432.
[23]Perlovich G L,Kurkov S V,Kinchin A N,et al.Thermodynamics of solutionsⅢ:C omparison of the solvation of(+)-naproxen with other N SAID s[J].European Journal of Pharmaceutical&Biopharmaceutics,2004,57(2):411-420.
[24]Kissinger H E.Reaction kinetics in differential thermal analysis[J].A nalytical C hemistry,1957,29(11):1702-1706.
[25]Sun X F,Qiu X Q,Li L P,et al.ZnO twin-cones:synthesis,photoluminescence,and catalytic decomposition of ammonium perchlorate[J].Inorganic C hemistry,2008,47(10):4146.
[26]Cheng MM,Li P,Duan X H,et al.A three-dimensional hierarchical dandelion-like HMX architecture formed at a liquid-liquid interface[J].C rystal Research&Technology,2018,53(3):1700226.
[28]王振宇.国外近年研制的新型不敏感单质炸药[J].含能材料,2003,11(4):227-230.WAN G Z hen-yu.D evelopment on some newinsensitive individual explosives abroad[J].C hinese Journal of Energetic Materials,2003,11(4):227-230.