含能增塑剂双(3-叠氮基-2,2-双(叠氮甲基)丙基)丙二酸酯的合成与性能

Synthesis and Properties of Energetic Plasticizer Bis(3-azido-2,2-bis(azidomethyl)propyl)malonate

以3-溴-2,2-双(溴甲基)-1-丙醇为起始物,经叠氮化反应、酯化反应,设计合成了新型含能增塑剂双(3-叠氮基-2,2-双(叠氮甲基)丙基)丙二酸酯(BAAMPM),并利用核磁共振和红外光谱对其进行了表征。研究了叠氮化反应和酯化反应的工艺条件,确定叠氮化反应的较佳反应条件为:n(TBrOH):n(NaN3)=1:3.3,反应温度为90~95℃,反应时间为12 h;酯化反应的较佳反应条件为:n(TAOH):n(MalAc):n(TsOH)=2:1:0.1 3,甲苯回流反应时间1 5 h,BAAMPM的收率和纯度分别可达到89.5%和98.5%。差示扫描量热法(DSC)测试表明BAAMPM的玻璃化转变温度为-58.3℃、热分解温度为231.0℃,根据GJB772A-1997方法测得BAAMPM的撞击感度为H50=40.9 cm、摩擦感度为28%,表明BAAMPM具有良好的低温性能和热稳定性以及较低的机械感度。此外,黏度和玻璃化转变温度表征结果显示,BAAMPM可显著降低聚叠氮缩水甘油醚(GAP)的黏度和玻璃化转变温度,并且随着BAAMPM添加比例的增加,GAP黏度的改善效果越加明显,GAP的玻璃化转变温度降低幅度增大,如BAAMPM/GAP(4/10)30℃下的黏度比GAP降低了52.65%,其玻璃化转变温度为-53.2℃,比GAP降低了4.1℃。因此,BAAMPM对GAP展现出较好的增塑效果。

By using 3-bromo-2,2-bis(bromomethyl)propan-1-ol(TAOH)as starting material,a novel multi-azido energetic plasticizer bis(3-azido-2,2-his(azidomethyl)propyl)malonate(BAAMPM)was synthesized via consecutive azidonation reaction and esterification reaction.All structures were characterized by NMR and IR spectrum.The influencing factors of azidonation reaction and esterification reaction were studied,and the optimal reaction conditions were determined as follows:for azidonation reaction,n(TBrOH):n(NaN3)=1:3.3,the reaction temperature is 90-95℃,and the reaction time is 12 h;for esterification reaction,n(TAOH):n(MalAc):n(TsOH)=2:1:0.13,refluxing in toluene for 15 h,and the yield and purity of BAAMPM are89.5%and 98.5%,respectively.For BAAMPM,the glass transition temperature(Tg)and thermal decomposition peak temperature were determined by differential scanning calorimetry(DSC)as-58.3℃and 231.0℃,respectively.According to the GJB772 A-1997 method,the impact sensitivity of BAAMPM was measured as Hso=40.9 cm,the friction sensitivity was 28%,which indicate that BAAMPM has good low temperature performance,good thermal stability as well as relatively low mechanical sensitivities.In addition,as the viscosity and glass transition temperature tests shown,BAAMPM could notably reduce the viscosity and glass transition temperature of glycidyl azide polymer(GAP).With the increase of the proportion of BAAMPM,the more obvious improvement for the viscosity of GAP,and the larger extent of lowering glass transition temperature of GAP are achieved.For example,the viscosity of BAAMPM/GAP(4/10)at 30℃is reduced by 52.65%compared with that of GAP,while its Tg is-53.2℃,4.1℃lower than that of GAP.Therefore,BAAMPM demonstrates good plasticizing effect on GAP.