双叠氮直链醚增塑剂的合成与性能

Synthesis and Properties of Diazido Linear Ether Plasticizers

分别以一缩二乙二醇(DEG)和二缩三乙二醇(TEG)为原料,经硝化、叠氮化反应合成了新型含能增塑剂1,5-二叠氮基-3-氧杂戊烷(AZDEGDN)和1,8-二叠氮基-3,6-二氧杂辛烷(AZTEGDN),优化了叠氮化反应条件,并采用红外光谱、核磁共振及元素分析对其结构进行了表征。结果表明,合成AZDEGDN的最佳反应条件为:叠氮化钠和一缩二乙二醇二硝酸酯(DEGDN)的摩尔比为2.7∶1,反应温度80℃,反应时间8 h;在此条件下,AZDEGDN收率为96.4%,纯度为99.1%。合成AZTEGDN的最佳反应条件为:叠氮化钠和二缩三乙二醇二硝酸酯(TEGDN)的摩尔比为2.5∶1,反应温度75℃,反应时间8 h;在此条件下,AZTEGDN收率为96.0%,纯度为99.2%。AZDEGDN的主要性能:生成焓912.5 kJ·mol-1,热分解温度249.3℃,摩擦感度0%,撞击感度64.6 cm;AZTEGDN的主要性能:生成焓898.1 kJ·mol-1,热分解温度256.1℃,摩擦感度0%,撞击感度151.4 cm。两者玻璃化温度均小于-100℃。

With diethylene glycol(DEG)and triethylene glycol(TEG)as starting materials,novel energetic plasticizers 1,5-diaz-ido-3-oxopentane(AZDEGDN)and 1,8-diazido-3,6-dioxooctane(AZTEGDN)were synthesized via nitration and azidation re-action.The conditions of azidation reaction were optimized.And the structures were characterized by infrared spectra,magnetic resonance spectra and element analysis.Results show that the optimal reaction conditions for the synthesis of AZDEGDN are the molar ratio of sodium azide and DEGDN of 2.7∶1,the reaction temperature of 80℃,and the reaction time of 8 h,under which the yield of AZDEGDN is 96.4%and the purity is 99.1%.The optimal reaction conditions for the synthesis of AZTEGDN are the molar ratio of sodium azide and TEGDN of 2.5∶1,the reaction temperature of 75℃,and the reaction time of 8 h,under which the yield of AZTEGDN is 96%and the purity is 99.2%.In addition,the enthalpy of formation,the decomposition temperature,the friction sensitivity and impact sensitivity of AZDEGDN are 912.5 kJ·mol-1,249.3℃,0%and 64.6 cm,respectively;while the main properties of AZTEGDN are 898.1 kJ·mol-1,256.1℃,0%and 151.4 cm,respectively.However,both of their glass transition temperatures are less than-100℃.