高等学校化学学报2012，Vol.33Issue(10)：2244-2248,5.DOI:10.7503/cjcu20120097
双核茂铁四氮唑的合成及对高氯酸铵热分解的催化作用
Synthesis of 2,2-Diferrocenylpropane-based Tetrazole and Its Catalysis Performance for Thermal Decomposition of Ammonium Perchlorate
摘要
Abstract
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 H 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.关键词
二茂铁衍生物/四唑杂环化合物/高氯酸铵/热分解Key words
Ferrocenyl derivatives/ Tetrazole/ Ammonium perchlorate/ Thermal decomposition分类
化学化工引用本文复制引用
廖文向,豆雅洁,王静,谢莉莉,林芬,袁耀锋..双核茂铁四氮唑的合成及对高氯酸铵热分解的催化作用[J].高等学校化学学报,2012,33(10):2244-2248,5.基金项目
国家自然科学基金(批准号:21172036)、福建省自然科学基金(批准号:2009J05028,2010J01036)、教育部留学回国人员科研启动基金(批准号:教外司留[2011]1568号)和福州大学光催化省部共建国家重点实验室培育基地开放课题资助. （批准号:21172036）
