Jia Jianhui, Chen Jian-Bo, Du Jianglong, Lian Cheng, Xu Silong, Liu Honglai, Li Shichun, Liu Yu
,Institute of Chemical Materials, China Academy of Engineering Physics, Mianyang 621900, P R China.
,Institute of Chemical Materials, China Academy of Engineering Physics, Mianyang 621900, P R China.
J Colloid Interface Sci. 2022 Dec 15;628(Pt A):426-436. doi: 10.1016/j.jcis.2022.07.140. Epub 2022 Jul 26.
Strongly hydrogen-bonded compounds such as 1,3,5-triamino-2,4,6‑trinitrobenzene (TATB, an important insensitive high explosive) have excellent stability, but poor solubilities to limit their recrystallization, purification and recycling. In this study, core-shell clusters based on symmetrical tetra-n-alkylammonium [TTA] are designed to provide an inner cavity to incorporate TATB, and thus the clusters can separate TATB from original hydrogen-bonded networks to increase largely the solubility. Based on this design, deep eutectic solvents (DESs) based on [TTA] cations are first developed to yield self-assembled core-shell clusters for solubilizing TATB. Ninety-nine DESs based on [TTA] were prepared by combining with halide ions and hydrogen bond donors, and TATB's solubility increases with the formation of core-shell clusters. Tetrabutyl ammonium ([TBA] )-based DES (CS-1) displays excellent dissolution toward TATB. Room-temperature solubility of TATB in CS-1 with 32.88 mg/mL is about 10 times higher than recently reported ionic liquids and approximately 470 times higher than DMSO. Compared to traditional solvents, CS-1 shows economical and high dissolution ability toward TATB. The dissolution mechanism is demonstrated by experimental characterizations and theoretical calculations. After forming Zundel-type complexes between TATB and F, the complexes as the core are surrounded by [TBA] as the shell to yield core-shell clusters through self-assembly of electrostatic interaction.
强氢键化合物，如1,3,5-三氨基-2,4,6-三硝基苯（TATB，一种重要的钝感高能炸药），具有出色的稳定性，但溶解度较差，这限制了它们的重结晶、纯化和循环利用。在本研究中，设计了基于对称四正烷基铵[TTA]的核壳簇，以提供一个内腔来容纳TATB，从而使这些簇能够将TATB与原有的氢键网络分离，大大提高其溶解度。基于这一设计，首先开发了基于[TTA]阳离子的低共熔溶剂（DESs），以产生用于溶解TATB的自组装核壳簇。通过与卤离子和氢键供体结合制备了99种基于[TTA]的DESs，TATB的溶解度随着核壳簇的形成而增加。基于四丁基铵（[TBA]）的DES（CS-1）对TATB表现出优异的溶解性能。TATB在CS-1中的室温溶解度为32.88 mg/mL，约为最近报道的离子液体的10倍，比二甲基亚砜（DMSO）高约470倍。与传统溶剂相比，CS-1对TATB表现出经济且高溶解能力。通过实验表征和理论计算证明了溶解机理。TATB与F形成尊德尔型配合物后，这些配合物作为核心被作为壳的[TBA]包围，通过静电相互作用自组装形成核壳簇。
