Wang Kuan, Chen Jian-Gang, Nie Zhan-Bin, Liu Zhao-Tie, Ji Yueping, Wang Bozhou, Liu Fengyi, Liu Zhong-Wen, Wang Wenliang, Lu Jian
Key Laboratory of Applied Surface and Colloid Chemistry (Ministry of Education), School of Chemistry & Chemical Engineering, Shaanxi Normal University Xi'an 710119 China
College of Chemistry and Chemical Engineering, Shaanxi University of Science & Technology Xi'an 710021 China.
RSC Adv. 2018 Apr 10;8(24):13301-13309. doi: 10.1039/c7ra12605k. eCollection 2018 Apr 9.
The hydrolysis mechanism and the kinetics of using 2-dinitromethylene-5,5-dinitropyrimidine-4,6-dione (NMP) to prepare the representative insensitive energetic material 1,1-diamino-2,2-dinitroethylene (FOX-7) in a nitric-sulfuric acid system are systematically investigated a density functional theory (DFT) method. The impact of the co-existing acidic group of HSO as well as the solvent effects of the mixed acids on the hydrolysis of NMP are elucidated and discerned, and the proposed catalysis and promotion of the hydrolysis of NMP with HSO are verified. The HSO -catalyzed hydrolysis pathway is more favorable than the direct pathway as well as the HO-catalyzed hydrolysis, indicating that HSO may be a promising catalyst for the preparation of FOX-7 in a mixed acid system. The present study is expected to provide a better understanding of the hydrolysis of NMP, and will significantly help with better preparation of FOX-7 and other nitro-energetic materials.
采用密度泛函理论（DFT）方法，系统研究了在硝酸 - 硫酸体系中，使用2 - 二硝基亚甲基 - 5,5 - 二硝基嘧啶 - 4,6 - 二酮（NMP）制备典型钝感含能材料1,1 - 二氨基 - 2,2 - 二硝基乙烯（FOX - 7）的水解机理及动力学。阐明并识别了共存的HSO酸性基团以及混合酸的溶剂效应对NMP水解的影响，验证了所提出的HSO对NMP水解的催化和促进作用。HSO催化的水解途径比直接途径以及HO催化的水解更有利，这表明HSO可能是混合酸体系中制备FOX - 7的一种有前景的催化剂。本研究有望提供对NMP水解的更好理解，并将显著有助于更好地制备FOX - 7和其他硝基含能材料。
