多环季胺类自燃离子液体的设计合成

发布时间：2018-07-03 00:53

本文选题：自燃离子液体 + 密度　；参考：《中国科学院大学(中国科学院过程工程研究所)》2017年硕士论文

【摘要】：在航天系统中,推进剂是动力核心。目前应用的肼类燃料易挥发、剧毒,亟待研发绿色替代品。离子液体具有低蒸汽压、低毒、高稳定性的特点,同时,部分离子液体还具有良好的"自燃"特性,成为极具潜力的新型推进剂燃料。但是自燃离子液体的密度有待进一步提高,从而实现推进剂装载量和比冲的提升。本文针对提高自燃离子液体密度,提出多环化和增加重原子的思路,设计合成新型离子液体,内容如下:设计合成了 1-氮-双环[2,2,2]辛烷类自燃离子液体,测试结果表明:分解温度230-322℃,密度 1.06-1.27 gcm-3,比冲 261.3.5-265.2 s,生成焓 7.8-431.1kJ mol-1,点火延迟时间14-186ms。其中,1-甲基-1-氮-双环[2,2,2]辛烷二氰胺盐(1.20g cm-3)密度高于单环同分异构化合物N-甲基-N-烯丙基吡咯二氰胺盐(1.05 gcm-3);1-炔丙基-1-氮-双环[2,2,2]辛烷二氰胺盐综合性能良好,如密度1.19gcm-3,比冲265.2s,生成焓431.1 kJ mol-1,点火延迟时间14 ms。设计合成了 1,4-二氮-双环[2,2,2]辛烷类自燃离子液体,测试结果表明:分解温度200-282℃,密度 1.10-1.31 gcm-3,生成焓 113.9-537.5 kJ mol-1 比冲 260.5-266.2s,点火延迟时间20-1053 ms。1,4-二氮-双环[2,2,2]辛烷类离子液体的热稳定性低于、密度高于相应的1-氮-双环[2,2,2]辛烷类离子液体。其中,1-炔丙基-1,4-二氮-双环[2,2,2]辛烷二氰胺盐密度(1.25gcm-3)高于相应的单环同分异构化合物1-乙烯基-3-丙基咪唑二氰胺盐(1.07 gcm-3)。设计合成了 5,7-二甲基-1,3-二氮金刚烷类离子液体,测试结果表明:分解温度157-305℃,密度 1.18-1.26 g cm-3,生成焓 11.9-140.9 kJ mol-1,比冲 257.8-263.8 s。其中含炔丙基支链的离子液体可以与白色发烟硝酸发生自燃反应。综上所述,本文在提高密度的指导思想下,设计合成了 1-氮-双环[2,2,2]辛烷类、1,4-二氮-双环[2,2,2]辛烷类、5,7-二甲基-1,3-二氮金刚烷类自燃离子液体,表征了所得离子液体的结构、玻璃化转变温度、热稳定性、自燃性及比冲,并进行了充分的讨论。测试结果证实三类离子液体具有相对高的密度,可达1.31 g cm-3,为高密度自燃离子液体发展提供了数据支撑和科学依据。
[Abstract]:The propellant is the dynamic core in the space system. The current hydrazine fuels are volatile, highly toxic and need to develop green substitutes. Ionic liquids have the characteristics of low vapor pressure, low toxicity and high stability. At the same time, some ionic liquids have good "spontaneous combustion" characteristics and become a potential new propellant fuel. The bulk density of the body needs to be further improved so as to achieve the propellant loading and specific impulse. In this paper, a new ionic liquid is designed and synthesized to improve the density of the spontaneous combustion ion liquid, put forward the idea of multi ring and increase heavy atoms. The contents are as follows: 1- nitrogen double ring [2,2,2] octane spontaneous combustion ionic liquid is designed and synthesized. The test results show that: The temperature is 230-322 C, the density 1.06-1.27 gcm-3, the specific impulse 261.3.5-265.2 s, the formation enthalpy 7.8-431.1kJ mol-1, the ignition delay time 14-186ms., and the 1- methyl -1- nitrogen double ring [2,2,2] octane two cyanamide salt (1.20g cm-3) is higher than the single ring isomeric compound of methylene propylene pyrrole two cyanamide salt (1.05); The comprehensive performance of [2,2,2] octane two cyanamide salt is good, such as density 1.19gcm-3, specific impulse 265.2s, formation enthalpy of 431.1 kJ mol-1, and ignition delay time 14 Ms. design and synthesis of 1,4- two nitrogen double ring [2,2,2] octane spontaneous combustion ionic liquid. The test results show that the decomposition temperature is 200-282 C, density 1.10-1.31 gcm-3, and the enthalpy 113.9-537.5 kJ is 2. 60.5-266.2s, the thermal stability of the ignition delay time 20-1053 ms.1,4- two nitrogen double ring [2,2,2] octane ionic liquids is lower than the corresponding 1- nitrogen double ring [2,2,2] octane ionic liquid. Among them, the 1- propargyl -1,4- two nitrogen double ring [2,2,2] octane two cyanamide density (1.25gcm-3) is higher than the corresponding mono ring isomeric compound 1- ethylene Based on the -3- propylimidazole two cyanamide salt (1.07 gcm-3), a 5,7- two methyl -1,3- two amantadine ionic liquid was designed and synthesized. The test results showed that the decomposition temperature was 157-305, 1.18-1.26 g cm-3, the formation enthalpy 11.9-140.9 kJ mol-1, and the ionic liquid containing the propargyl chain in the specific impulse 257.8-263.8 S. could occur with the white smoke nitric acid. In summary, under the guidance of improving the density, this paper designs and syntheses 1- nitrogen double ring [2,2,2] octane, 1,4- two nitrogen double ring [2,2,2] octane, 5,7- two methyl -1,3- two nitrogen amantane spontaneous combustion ionic liquid, which characterizing the structure of the ionic liquid, glass transition temperature, thermal stability, spontaneous combustion and specific impulse, and advance. The results show that the three kinds of ionic liquids have relatively high density and can reach 1.31 g cm-3, which provides data support and scientific basis for the development of high density spontaneous combustion ionic liquids.
【学位授予单位】：中国科学院大学(中国科学院过程工程研究所)
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：V511;O645.1

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