Ferrocenyl Ionic Compounds Based on 5-Ferrocenyl-1H-tetrazole. Synthesis, Characterization, Migration, and Catalytic Effects During Combustion†
Ferrocenyl Ionic Compounds Based on 5-Ferrocenyl-1H-tetrazole. Synthesis, Characterization, Migration, and Catalytic Effects During Combustion†
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DOI：
10.1002/zaac.201500690
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发表时间：
2016
期刊：
影响因子：
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通讯作者：
Gao Xiaoni;A. Ting;Jizhen Li;F. Zhao;X. Fan;Xinyan Li;Guofang Zhang;Ziwei Gao
中科院分区：
文献类型：
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作者：
Gao Xiaoni;A. Ting;Jizhen Li;F. Zhao;X. Fan;Xinyan Li;Guofang Zhang;Ziwei Gao
合成了由5-二茂铁基四唑阴离子和胍或1-烷基-3-甲基咪唑阳离子组成的二茂铁基离子化合物，并通过1H NMR，13 C NMR，UV/维斯光谱和元素分析进行了表征.通过单晶X射线衍射进一步证实了四种化合物的分子结构。TG和DSC分析结果表明，部分化合物具有较高的热稳定性。循环伏安法研究表明，该化合物表现出二茂铁基的氧化还原波，被认为是不可逆的氧化还原体系。迁移研究表明，这些化合物的迁移趋势远低于广泛用于复合固体推进剂的2，2-双（乙基二茂铁基）丙烷（Catocene）。用DSC和TG技术研究了它们对高氯酸铵（AP）、1，3，5-三硝基-1，3，5-三氮杂环己烷（RDX）和1，2，5，7-四硝基-1，3，5，7-四氮杂环辛烷（HMX）热分解反应的催化性能。大多数化合物在AP和RDX的热降解中表现出很高的催化效率。含胍化合物1-3的放热性能较好，这表明富氮部分有利于提高某些含能材料的放热性能。这些胍盐可作为二茂铁基燃速催化剂候选物用于复合固体推进剂。
Ferrocenyl ionic compounds, consisting of the 5-ferrocenyltetrazolate anion and a guanidinium or a 1-alkyl-3-methylimidazolium cation, were synthesized and characterized by 1H NMR, 13C NMR, and UV/Vis spectroscopy, as well as elementary analysis. The molecular structures of four compounds were additionally confirmed by single-crystal X-ray diffraction. Results of the TG and DSC analyses showed that some compounds display high thermal stability. Cyclic voltammetry investigations suggested that the compounds exhibit redox waves for the ferrocenyl groups and are considered as irreversible redox systems. Migration studies revealed that migration trends of the compounds are much lower than that of 2, 2-bis(ethylferrocenyl)propane (Catocene), extensively used in composite solid propellants. Their catalytic performances for thermal decomposition of ammonium perchlorate (AP), 1, 3,5-trinitro-1, 3,5-triazacyclohexane (RDX), and 1, 2,5, 7-tetranitro-1, 3,5, 7-tetraazacyclooctane (HMX) were evaluated by DSC and/or TG techniques. Most of the compounds exhibit high catalytic efficiency in the thermal degradation of AP and RDX. Those of the guanidine-containing compounds 1–3 are better, implying that nitrogen-rich moieties are beneficial to enhancing released heats of some energetic materials. These guanidine salts could be used as ferrocene-based burning rate catalyst candidates in composite solid propellants.