Zhang Junlin, Liu Yingzhe, Zhou Jing, Bi Fuqiang, Wang Bozhou
Xi'an Modern Chemistry Research Institute Xi'an, 710065, P. R. China.
Department of Chemistry, Technische Universität München, 85748, Garching bei München, Germany.
Chempluschem. 2019 Jan;84(1):92-97. doi: 10.1002/cplu.201800523. Epub 2018 Dec 7.
The replacement of traditional polynitroarylenes by their fluorinated derivatives has attracted great attention due to the improvements on detonation performance caused by the fluorine effect. A straightforward synthesis of three novel fluorinated nitrotoluenes with different degrees of nitration was achieved under selected high temperatures. The fluorine exerted remarkable influence on the nitration process through the electron-withdrawing effect and a mechanism of the transformation was proposed according to the experimental results. Thermal decomposition behavior of the fluorinated nitrotoluenes was investigated by differential scanning calorimetry and all the compounds showed ideal low melt points for the melt-cast process. X-ray analysis of the fluorinated derivatives were carried out as well as density functional calculations to establish the electronic density and electrostatic potential on the molecular surface of the optimized structures. The good thermal and detonation properties make the newly developed fluorinated nitrotoluenes possible replacements for trinitrotoluene and dinitrotoluene in the formation of melt-cast energetic materials.
由于氟效应导致爆轰性能的改善，用其氟化衍生物替代传统的多硝基芳烃引起了极大关注。在选定的高温下，实现了三种不同硝化程度的新型氟化硝基甲苯的直接合成。氟通过吸电子效应在硝化过程中产生了显著影响，并根据实验结果提出了转化机理。通过差示扫描量热法研究了氟化硝基甲苯的热分解行为，所有化合物在熔铸过程中均表现出理想的低熔点。对氟化衍生物进行了X射线分析以及密度泛函计算，以确定优化结构分子表面的电子密度和静电势。良好的热性能和爆轰性能使得新开发的氟化硝基甲苯有可能在熔铸含能材料的形成中替代三硝基甲苯和二硝基甲苯。
