Liu Tianlin, Qi Xiujuan, Wang Binshen, Jin Yunhe, Yan Chao, Wang Yi, Zhang Qinghua
Research Center of Energetic Material Genome Science, Institute of Chemical Materials, China Academy of Engineering Physics (CAEP), Mianyang, 621900, P.R. China.
Sichuan Co-Innovation Center for New Energetic Materials, Southwest University of Science and Technology, Mianyang, 621900, P.R. China.
Chemistry. 2018 Jul 17;24(40):10201-10207. doi: 10.1002/chem.201801593. Epub 2018 Jun 19.
The design and synthesis of new hypergolic ionic liquids (HILs) as replacements for toxic hydrazine derivatives have been the focus of current academic research in the field of liquid bipropellant fuels. In most cases, however, the requirements of excellent ignition performances, good hydrolytic stabilities, and low synthetic costs are often contradictory, which makes the development of high-performance HILs an enormous challenge. Here, we show how a fuel-rich boranophosphate ion was rationally designed and used to synthesize a series of high-performance HILs with excellent comprehensive properties. In the design strategy, we introduced the {BH } moiety into the boranophosphate ion for improving the self-ignition property, whereas the complexation of boron and phosphite was used to improve the hydrolytic activity of the borohydride species. As a result, these boranophosphate HILs exhibited wide liquid operating ranges (>220 °C), high densities (1.00-1.10 g cm ), good hydrolytic stabilities, and short ignition delay times (2.3-9.7 milliseconds) with white fuming nitric acid (WFNA) as the oxidizer. More importantly, these boranophosphate HILs could be readily prepared in high yields from commercial phosphite esters, avoiding complex and time-consuming synthetic routes. This work offers an effective strategy of designing boranophosphate HILs towards safer and greener hypergolic fuels for liquid bipropellant applications.
新型自燃离子液体(HILs)作为有毒肼衍生物的替代品的设计与合成一直是液体双组元推进剂燃料领域当前学术研究的重点。然而,在大多数情况下,优异的点火性能、良好的水解稳定性和较低的合成成本这些要求往往相互矛盾,这使得高性能HILs的开发成为一项巨大挑战。在此,我们展示了如何合理设计一种富燃料的硼磷酸根离子,并用于合成一系列具有优异综合性能的高性能HILs。在设计策略中,我们将{BH }部分引入硼磷酸根离子以改善自燃性能,而硼与亚磷酸酯的络合用于提高硼氢化物物种的水解活性。结果,这些硼磷酸根HILs表现出较宽的液体工作温度范围(>220 °C)、高密度(1.00 - 1.10 g cm )、良好的水解稳定性,并且以发烟硝酸(WFNA)作为氧化剂时具有较短的点火延迟时间(2.3 - 9.7毫秒)。更重要的是,这些硼磷酸根HILs可以从商业亚磷酸酯以高产率轻松制备,避免了复杂且耗时的合成路线。这项工作为设计硼磷酸根HILs提供了一种有效的策略,以用于更安全、更绿色的液体双组元推进剂自燃燃料应用。