双核茂铁四氮唑的合成及对高氯酸铵热分解的催化作用

首先以二茂铁为原料合成丙基桥联的双聚二茂铁(DFP), 经甲酰化得到丙基桥联的双聚二茂铁甲醛(DFP-CHO, 1), 再与NH₂OH·5HCl进行缩合反应得到双核二茂铁肟(2), 然后脱水得到丙基桥联双聚二茂铁甲腈(3), 最后在(n-C₄H₉)₃SnCl 的催化作用下与NaN₃进行[2+3]环加成反应, 生成目标产物丙基桥联双聚二茂铁四唑(4); 通过¹H NMR, FTIR和ESI-MS对目标产物的结构进行了表征. 利用差示扫描量热分析(DSC)和热重(TG)分析研究了这2个双聚二茂铁氮杂衍生物的燃速催化性能, 结果表明, 通过添加质量分数为5%的丙基桥联双聚二茂铁氮杂化合物3和4均使高氯酸铵(AP)的热分解温度降至100℃左右.

Synthesis of 2,2-Diferrocenylpropane-based Tetrazole and Its Catalysis Performance for Thermal Decomposition of Ammonium Perchlorate

Ferrocenyl derivatives as burning rate catalysts for hydroxyl-terminated polybutadiene(HTPB) have been used widely. Among them, binuclear ferrocenyl compounds perform much better due to good thermal stability, low volatility and migration so as to gradually be an important kind of burning rate catalyst. Research showed that N-heterocyclic energetic material compared to traditional ones had excellent catalytic effect and can be easily controlled through changing anion or cation. Considering performance superposition principle, a tetrazole and binuclear ferrocenyl should be combined into a molecule for mixing both excellences. In order to reduce volatility, migration and energy losses of such catalysts, groups containg-N can be introduced to enhance molecule polarity and strengthen van der Waals force between them and propellant, which are in favor of formation of hydrogen bond and increase of viscoplastic of HTPB within kept of high iron content of catalyst as a result of high combustion catalytic performance. This paper provides a multistep procedure for the preparation of 5-(2,2-diferrocenylpropane)-1H-tetrazole(4). After stepwise biopolymer and Vilsmeier formylation, 2,2-diferrocenylpropane carbaldehyde(1) was synthesized from ferrocene with moderate yield, and then compound 1 was transformed into 2,2-diferrocenylpropane carbaldehyde oxime(2). Dehydration of the oxime gave 2,2-diferrocenylpropane nitrile(3). Finally, compound 4 was obtained via click reaction([2+3] cycloaddi-tion) between compound 3 and sodium azide. Structures of the target compounds were characterized by 1H NMR, FTIR and mass spectrum. Electrochemical properties of the target compounds were investigated by cyclic voltammetry and differential pulse voltammetry. Relationship between electrochemical behavior of multi-component redox and structure was discussed. Thermal decomposition characteristics of ammonium perchlorate (AP) with 5%(mass fraction) of compound 3 or 4 were investigated by differential scanning calorimetry (DSC) and thermogravimetry (TG) analysis. The results showed that the final exothermic peak temperature of AP was reduced by about 100℃ and compounds 3 and 4 had good combustion catalytic characteristics on AP.