5-肼基四唑高氯酸含能配合物的合成、表征及性能
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摘要
以5-肼基四唑(5-HT)为配体,制备5种含能配合物[Cd(HT)_6](ClO_4)_2(1),[Zn(HT)6](ClO_4)_2(2),[Ni(HT)_3](ClO_4)_2(3),[Co(HT)_6](ClO_4)_2(4),[Mn(HT)_6](ClO_4)_2(5)。采用元素分析和傅里叶变换红外光谱对5种配合物进行结构表征。通过差示扫描量热分析(DSC)研究其热分解性能,测试了其摩擦感度和撞击感度。在B3LYP/6-311++g**水平上理论研究了5-HT电子结构性质、自然键轨道电荷以及分子前线轨道。结果表明,5种配合物具有较高热稳定性,分解温度均高于200℃。5-HT四唑环上的N(3)和N(4)原子更容易同时参与金属原子配位,形成以5-肼基四唑为配体的配位化合物。90°摆角、1.96 MPa条件下,配合物4的摩擦感度为96%,800 g落锤下,撞击感度H50为25 cm,其机械感度与肼基四唑汞(HTMP)和高氯酸·四氨·双(5-硝基四唑)合钴(Ⅲ)(BNCP)相当,有望应用于起爆药领域。
Five coordination complexes[Cd(HT)_6](ClO_4)_2(1),[Zn(HT)_6](ClO_4)_2(2),[Ni(HT)_3](ClO_4)_2(3),[Co(HT)_6](ClO_4)_2(4),[Mn(HT)_6](ClO_4)_2(5) with 5-hydrazinotetrazole(5-HT) as ligands were prepared.Their structures were characterized by elemental analysis and FT-IR.The thermal decompositions were studied by differential scanning calorimetry and the impact sensitivity and friction sensitivity were also tested.The theoretical calculations of the electronic structure,natural bond orbital charge and frontier orbital energy of 5-HT were studied at B3LYP/6-311 + +g** level.Results show that the five complexes have good thermal stability,and the decomposition temperatures are above 200 ℃.N(3) and N(4) atoms of tetrazole ring are easier to coordinate with metal atoms.The friction sensitivity of complex 4 is 96%(90°,1.96 MPa) and H_(50) is 25 cm with the 800 g drop hammer,which is similar to that of HTMP and BNCP,indicating a promising application in the field of primary explosive.
Five coordination complexes[Cd(HT)_6](ClO_4)_2(1),[Zn(HT)_6](ClO_4)_2(2),[Ni(HT)_3](ClO_4)_2(3),[Co(HT)_6](ClO_4)_2(4),[Mn(HT)_6](ClO_4)_2(5) with 5-hydrazinotetrazole(5-HT) as ligands were prepared.Their structures were characterized by elemental analysis and FT-IR.The thermal decompositions were studied by differential scanning calorimetry and the impact sensitivity and friction sensitivity were also tested.The theoretical calculations of the electronic structure,natural bond orbital charge and frontier orbital energy of 5-HT were studied at B3LYP/6-311 + +g** level.Results show that the five complexes have good thermal stability,and the decomposition temperatures are above 200 ℃.N(3) and N(4) atoms of tetrazole ring are easier to coordinate with metal atoms.The friction sensitivity of complex 4 is 96%(90°,1.96 MPa) and H_(50) is 25 cm with the 800 g drop hammer,which is similar to that of HTMP and BNCP,indicating a promising application in the field of primary explosive.
引文
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[2]Huynh M,Michael A H,Thomas J M,et al.Green primaries:environmentally friendly energetic complexes[J].Environmental Sciences,2006,103(14):5409-5412.
[3]盛涤伦,马凤娥,孙飞龙,等.BNCP起爆药的合成及其主要性能[J].含能材料,2000,8(3):100-103.SHENG Di-1un,MA Feng-e,SUN Fei-long,et al.Study on synthesis and main poroperties of BNCP[J].Chinese Journal of EnergeticMaterials(Hanneng Cailiao),2000,8(3):100-103.
[4]徐松林,阳世清,岳守体,等.偶氮四唑类高氮含能化合物的合成及表征[J].火炸药学报,2005,28(3):52-54.XU Song-lin,YANG Shi-qing,YUE Shou-ti,et al.Synthesis and characterization of high-nitrogenenergetic compounds derived from azotetrazolate[J].Chinese Journal of Explosives&Propellants,2005,28(3):52-54.
[5]周素芹,居学海,肖鹤鸣,等.四唑与水二聚体相互作用的理论研究[J].火炸药学报,2005,28(4):1-4,13.ZHOU Su-qin,JU Xue-hai,XIAO He-ming,et al.T heoreticalstudy on intermolecular interactions oftetrazole-waterdimers[J].Chinese Journal of Explosives&Propellants,2005,28(3):52-54.
[6]Joo Y H,Twamley B.Carbonyl and oxalyl bridged bis(1,5-diaminotetrazole)-based energetic salts[J].Chemistry:a,European Journal,2009,15(36):9097-9104.
[7]SHANG Jing,ZHANG Jian-guo,ZHANG Tong-lai,et al.Theoretical study of energetic complexes(Ⅲ):bis-(5-nitro-2htetrazolato-N2)tetraammine cobalt(Ⅲ)perchlorate(BNCP)and its transition met al(Ni/Fe/Cu/Zn)perchlorate analogues[J].Chinese Journal of Chemistry,2012,30(7):1624-1630.
[8]盛涤伦,朱雅红,蒲彦利,等.新一代起爆药设计与合成研究进展[J].含能材料,2012,20(3):263-272.SHENG Di-lun,ZHU Ya-hong,PU Yan-li,et al.Development of a new-generation primary explosives designing and synthesis[J].Chinese Journal of Energetic Materials(Hanneng Cailiao),2012,20(3):263-272.
[9]David A,Dixon D F,Karl O C,et al.Enthalpies of formation of gas-phase N_3,N_3~-,N_5~+,and N_5~-from Ab initio molecular orbital theory,stability predictions for N_5~+,N_3~-and N_5~+,N_5~-,and experimental evidence for the instability of N_5~+,N_3~-[J].Journal of the American Chemical Society,2004,126(3):834-843.
[10]Fischer N,Klapotke T M,Piercey D G,et al.Hydroxylammonium 5-nitriminotetrazolates[J].Zeitschrift fur Anorganische and Allgemeine Chemie,2012,638(2):302-310.
[11]Fischer N,Joas M,Klapotke T M,et al.Transition met al complexes of 3-amino-1-nitroguanidine as laser ignitible primary explosives:structures and properties[J].Inorganic Chemistry,2013,52(23):13791-13802.
[12]Klapotke T M,Piercey D G.1,1'-azobis(tetrazole):a highly energetic nitrogen-rich compound with a N10 chain[J].InorganicChemistry,2011,50(7):2732-2734.
[13]Joo Y H,Twamley B.Energetic nitrogen-rich derivatives of 1,5-aiaminotetrazole[J].Angew Chem,2008,47(33):6236-6239.
[14]李志敏,张建国,刘俊伟,等.固体火箭技术[J].1,5-二氨基四唑含能配合物的制备、表征及其催化性能研究,2011,34(1):79-85.LI Zhi-min,ZHANG Jian-guo,LIU Jun-wei,et al.Synthesis,characterization and catalytic activity of energetic complexes based on 1,5-diaminotetrazole[J].Journal of Solid Rocket Technology,2011,34(1):79-85.
[15]Skocypec R D,Mahoney A R,Glass M W,et al.Modeling laser iginition of explosives and pymtechnicseffects and characterization of radiative transfer[C]//Proceedings of thel5 th International Pyrotechnic Seminar,1990:877-894.
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[17]Ilyushin M A,Tselinsky I V,Bachurina I V,et al.Laser initiation of complex perchlorates of d-metals with heterocyclic ligands[J].Chinese Journal of Energetic Materials(Hanneng Cailiao),2006,14(6):401-405.
[18]彭蕾,李玉川,杨雨璋,等.双环和多环四唑含能化合物的合成研究进展[J].有机化学,2012(4):667-676.PENG Lei,LI Yu-chuan,YANG Yu-zhang,et al.Research progress in synthesis of energetic compounds of bicyclo-and multicyclo-tetrazoles[J].Chinese Journal of Organic Chemistry,2012(4):667-676.
[19]阳世清,岳守体.国外四嗪四唑类高氮含能材料研究进展[J].含能材料,2003,11(4):231-235.YANG Shi-qing,YU E Shou-ti.Progress in High-nitrogen energetic materials derived from tetrazine and tetrazole[J].Chinese Journal of Energetic Materials(Hanneng Cailiao),2003,11(4):231-235.
[20]朱雅红,盛涤伦,陈利魁,等.含能中间体5-肼基四唑的合成及表征[J].火炸药学报,2008,31(6):39-41.ZHU Ya-hong,SHENG Di-lun,CHEN Li-kui,et al.Synthesis and characterization of energetic intermediate 5-hydrazinotetrazole[J].Chinese Journal of Explosives&Propellants,2008,31(6):39-41.
[21]朱雅红,盛涤伦,杨斌,等.激光敏感起爆药高氯酸·5-肼基四唑汞的合成和性能[J].含能材料,2009,17(2):169-172.ZHU Ya-hong,SHENG Di-lun,YANG Bin,et al.Synthesis and properties of laser sensitivity primary explosive 5-hydrazinotetrazolemercury perchlorate[J].Chinese Journal of Energetic Materials(Hanneng Cailiao),2009,17(2):169-172.
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[25]Lu T,Multiwfn.version 1.4:http://multiwfn.codeplex.com/.[2015,03,13]