Study on the antioxidant property of calixarene in high density hydrocarbon fuel JP-10
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摘要: 高密度吸热型碳氢燃料在热、催化等作用下会与溶解氧发生氧化反应，导致使用性能降低，进而威胁飞行安全。杯芳烃在与常用的酚类抗氧剂分子结构相似的前提下，拥有更好的热稳定性，可以在苛刻的工作环境中对燃料起到抗氧化作用。本实验合成了具有油溶性的C-十一烷基间苯二酚杯[4]芳烃(C11-C[4]R)，考察其在高密度碳氢燃料JP-10中的抗氧化性能，并与商用抗氧剂2,6-二叔丁基-4-甲基苯酚(BHT)、四[β-(3,5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯(L-1010)和β-(3,5-二叔丁基-4-羟基苯基)丙酸十八碳醇酯(L-1076)等的抗氧化效果进行对比。高压差示扫描量热仪(PDSC)评价结果显示，四种抗氧化剂的效果排序为：C11-C [4] R > BHT > L-1010 > L-1076。还采用静态釜加速氧化法研究了JP-10的氧化反应历程，提出了C11-C[4]R在JP-10中的抗氧化机理。Abstract: Since the 21st century, hypersonic flight technology has attracted much attention. When the aircraft is flying at a high Mach number, a large amount of aerodynamic heat is generated between the air and the aircraft due to friction, resulting in a rapid increase in the temperature of the aircraft subsystem, exceeding the range that the material can withstand, affecting the flight safety of the aircraft. In order to meet the thermal management needs, an integrated cooling approach combining heat transfer and combustion has been introduced. This method utilizes hydrocarbon fuels both as propellants and coolants to absorb the excess heat from the aircraft's high-temperature components, thereby enhancing energy efficiency and managing the thermal conditions of high-speed aircraft. Fuels that satisfy this concept are called endothermic hydrocarbon fuels. However, these fuels are prone to oxidation due to heat, oxygen, and catalysis during storage and use, leading to the formation of insoluble gums and degraded performance, which may even clog the fuel system, endangering flight safety. Thus, suppressing the oxidation process of high-density endothermic hydrocarbon fuels is crucial for fuel storage and usage. Common methods to improve the oxidation stability of fuels include surface treatment, fuel deoxidation, and the addition of antioxidants to the fuel. Among these methods, adding antioxidants is one of the most commonly used methods. Hindered phenolic antioxidants are favored for their cost-effectiveness, but small molecule antioxidants like tert-butylhydroquinone (TBHQ) and butylated hydroxytoluene (BHT) suffer from sublimation at high temperatures, resulting in poor oxidation resistance. Conversely, commercial macromolecular antioxidants, such as L-1010 and L-1076, fall short of the antioxidant needs of hydrocarbon fuels due to their limited properties. In order to make up for the shortage of commercial hindered phenolic antioxidants, researchers have focused on the development of new antioxidants with high temperature resistance and significant antioxidant effect. Calixarenes, with their structural features of hindered phenols, are seen as potential antioxidants, Especially, the calixarene synthesized with resorcinol as monomer has high phenolic hydroxyl content, which can quench the oxygen free radicals produced in the process of fuel oxidation by providing more abundant hydrogen free radicals, thus has better oxidation resistance. However, reports on using calixarenes for enhancing the oxidation resistance of high-density hydrocarbon fuels remain scarce. In this paper, C-undecylcalix[4]resorcinarene(C11-C[4]R) was synthesized by using resorcinol and dodecanal, and its oxidation resistance in high-density hydrocarbon fuel JP-10 was investigated.and compared with several commercial antioxidants:2,6-di-tert-butyl-4-methylphenol, tetra [β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid] pentaerythritol ester and β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid octadecyl ester. The results of high pressure differential scanning calorimeter (PDSC) showed that the effect of four antioxidants ranked as follows: C11-C[4]R > BHT > L-1010 > L-1076. In addition, the oxidation consumption process of four hindered phenolic antioxidants in JP-10 was analyzed from the perspective of kinetics, and the oxidation consumption rate constant was calculated. The results showed that the reaction rate constant of C11-C [ 4 ] was the smallest and the consumption rate in JP-10 was the slowest. Besides, the oxidation reaction process of JP-10 was also studied using the static kettle accelerated oxidation method. Based on these findings, a potential antioxidant mechanism of C11-C[4]R in JP-10 was proposed.
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Key words:
- calixarene /
- antioxidant /
- PDSC /
- antioxidant mechanism
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图 5 四种受阻酚抗氧剂热稳定性对比
Figure 5 Comparative study on thermal stability of four hindered phenol antioxidants
图 6 JP-10氧化诱导时间以及氧化起始温度随抗氧剂添加量的变化
Figure 6 The change trend of IP and OT of JP-10 with the addition of antioxidant
图 7 四种受阻酚抗氧剂在JP-10中的氧化动力学拟合
Figure 7 Oxidation kinetics fitting of four hindered phenol antioxidants in JP-10
图 10 静态釜加速氧化法下四种抗氧剂对JP-10氧化程度以及主要含氧产物生成趋势影响
Figure 10 The effects of four antioxidants on the oxidation degree of JP-10 and the formation trend of main oxygen-containing products under static kettle accelerated oxidation method
图 11 添加抗氧剂后JP-10氧化残液基础物性变化趋势
Figure 11 The change trend of basic physical properties of JP-10 oxidation residue after adding antioxidants
图 12 杯芳烃抑制碳氢燃料氧化机理示意图
Figure 12 Chart of inhibition mechanism of hydrocarbon fuel oxidation by calixarene
表 1 四种受阻酚类抗氧剂在JP-10中氧化消耗动力学参数
Table 1 Kinetic parameters of oxidation consumption of four hindered phenolic antioxidants in JP-10
Sample k/min−1 cr/(mg·L−1) R2 L-1076 0.370 73.4 1.00 L-1010 0.340 44.4 0.99 BHT 0.298 51.1 1.00 C11-C[4]R 0.155 75.3 0.99 
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