硝基氰胺乙烯基咪唑过渡金属配合物的合成及结构与性能分析  

Transition Metal Complexes of Nitrocyanamide Vinylimidazole:Syntheses,Structures and Performances

作　　者：葛明成 钟野 杨学军 祝贺 张建国[1] 李志敏[1] GE Ming-cheng;ZHONG Ye;YANG Xue-jun;ZHU He;ZHANG Jian-guo;LI Zhi-min(State Key Laboratory of Explosion Science and Technology,Beijing Institute of Technology,Beijing 100081,China;Anhui Hongxing Electrical Polytron Technologies Co.Ltd.,Hefei 231135,China;Shanxi Jiangyang District Khingan Civilian Explosive Equipment Co.Ltd.,Taiyuan 030041,China)

机构地区：[1]北京理工大学爆炸科学与技术国家重点实验室,北京100081 [2]安徽红星机电科技股份有限公司,安徽合肥231135 [3]山西江阳兴安民爆器材有限公司,山西太原030041

出　　处：《火炸药学报》2024年第2期137-144,I0002,共9页Chinese Journal of Explosives & Propellants

基　　金：国家自然科学基金(No.21805008)。

摘　　要：为探索固体推进剂含能燃烧催化剂,以硝基氰胺根(NCA)为阴离子、1-乙烯基咪唑(VIM)为配体,过渡金属Mn、Co、Ni、Cu为中心离子,制备出4种新型含能配合物,结构式分别为[Mn(VIM)_(4)](NCA)_(2)(配合物1)、[Co(VIM)_(4)](NCA)_(2)(配合物2)、[Ni(VIM)_(4)](NCA)_(2)(配合物3)、[Cu(VIM)_(4)](NCA)_(2)(配合物4);通过元素分析、红外光谱(FT-IR)、X射线晶体衍射(XRD)、感度测试和氧弹量热法对其结构和物理化学性质进行了表征;用差示扫描量热法(DSC)和热重分析(TGA)研究了配合物1~配合物4的热分解过程,并利用DSC研究了配合物1~配合物4对高氯酸铵(AP)热分解的催化作用。结果表明,配合物1~配合物4均具有较高的能量密度,其中配合物2质量能量密度(E_(g))为19.00 kJ/g,体积能量密度(E_(v))为27.18 kJ/cm^(3);4种配合物的摩擦感度值均不小于288 N,撞击感度值均大于40 J。加入质量分数5%催化剂的AP样品高温分解温度均得到提前,放热量均显著提高;其中配合物2表现出最好的催化性能,加入配合物2的AP放热量升高至1564 J/g,分解温度提前了62.0℃,活化能降至142.9 kJ/mol,表明配合物2具有作为固体推进剂含能燃烧催化剂的潜力。In order to explore energy combustion catalyst for solid propellant,four new coordination compounds were synthesized using nitrocyanamide(NCA)as anion,1-vinylimidazole(VIM)as ligand and transition-metal Mn,Co,Ni and Cu as central ions.Their structures formula were[Mn(VIM)_(4)](NCA)_(2)(complex 1),[Co(VIM)_(4)](NCA)_(2)(complex 2),[Ni(VIM)_(4)](NCA)_(2)(complex 3),and[Cu(VIM)_(4)](NCA)_(2)(complex 4).The structure and physicochemical properties of the compounds were characterized by elemental analysis,infrared spectroscopy(IR),X-ray crystal diffraction(XRD),sensitivity test and oxygen bomb calorimetry.The thermal decomposition of the energetic complexes were studied by differential scanning calorimetry(DSC)and thermogravimetric analysis(TGA).The catalytic effect of complex 1—complex 4 on the thermal decomposition of ammonium perchlorate(AP)was investigated by DSC.The results showed that complex 1—complex 4 have high energy density,in which mass energy density and bulk energy density are 19.00 kJ/g and 27.18 kJ/cm^(3)of complex 2.The friction sensitivity of the four complexes was greater than 288 N and the impact sensitivity of the four complexes was greater than 40 J.The high temperature decomposition temperature of AP samples with 5%catalyst was advanced,and the heat release was significantly increased.Among them,complex 2 showed the best catalytic performance.The AP heat release of complex 2 increased to 1564 J/g and the decomposition temperature advanced by 62.0℃.The activation energy decreased to 142.9 kJ/mol,indicating that complex 2 has the potential as a catalyst for energetic combustion of solid propellant.

关 键 词：高分子化学 含能配合物 固体推进剂 燃烧催化剂 热分解 

分 类 号：TJ55[兵器科学与技术—军事化学与烟火技术] O63[理学—高分子化学]