含能增塑剂2,2-偕二硝基丙基三氟丙酸酯的合成及性能  

Synthesis and Properties of Energetic Plasticizer 2,2-Dinitropropyl Trifluoropropanoate

作　　者：赵宝东 刘亚静[1] 潘永飞[1] 刘卫孝[1] 高福磊[1] 汪营磊[1,2] ZHAO Baodong;LIU Yajing;PAN Yongfei;LIU Weixiao;GAO Fulei;WANG Yinglei(Xi'an Modern Chemistry Research Institute,2.State Key Laboratory of Fluorine&Nitrogen Chemicals,Xi'an 710065,China)

机构地区：[1]西安近代化学研究所 [2]西安近代化学研究所氟氮化工资源高效开发与利用国家重点实验室,西安710065

出　　处：《高等学校化学学报》2021年第9期2815-2823,共9页Chemical Journal of Chinese Universities

基　　金：国家自然科学基金(批准号:21875185,21173163)资助.

摘　　要：以硝基乙烷为原料,经缩合、氧化及酯化反应,设计合成了含能增塑剂2,2-偕二硝基丙基三氟丙酸酯(DNPTFP);利用核磁共振波谱、红外光谱和元素分析对其结构进行了表征.优化了DNPTFP的合成工艺,确定酯化反应的较佳反应条件:以甲苯为反应溶剂,n(2,2-偕二硝基丙醇)∶n(三氟丙酸)=1∶1.10,催化剂浓硫酸的质量分数为5.0%,反应温度110℃,反应时间10 h.在此条件下,DNPTFP的收率和纯度分别为75.2%和99.0%.热分析测试结果表明,DNPTFP的玻璃化转变温度为−80.5℃,热分解温度为267.59℃;机械感度测试结果表明,DNPTFP的撞击感度为H50=125.9 cm,摩擦感度为0,说明DNPTFP具有良好的低温性能、热稳定性及较低的机械感度.此外,相溶性试验、黏度及玻璃化转变温度测试结果表明,DNPTFP与聚叠氮缩水甘油醚(GAP)相溶性良好,DNPTFP可显著调控GAP的黏度和玻璃化转变温度,并且随其含量增加黏流活化能逐步降低,增塑效率逐步升高.因此,DNPTFP对GAP展现出优良的增塑效果,在GAP基火炸药配方中有良好的应用前景.With nitroethane as starting material,energetic plasticizer 2,2-dinitropropyl trifluoropropanoate(DNPTFP)was designed and synthesized via condensation reaction,oxidation reaction and esterification reaction.Its structure was characterized and confirmed by means of nuclear magnetic resonance(NMR),Fourier transform infrared spectroscopy(FTIR)and elemental analysis.Optimization on the synthesis process of DNPTFP was conducted,and the optimal reaction conditions for the esterification reaction were determined as follows:taking toluene as reaction solvent,n(2,2-dinitropropan-1-ol)∶n(trifluoropropanoic acid)=1∶1.10,the addition of concentrated H_(2)SO_(4) catalyst was 5.0%(mass fraction),the reaction temperature was 110℃,the reaction time was 10 h,and the yield and purity of DNPTFP was 75.2%and 99.0%,respectively.Thermal analysis determined that the glass transition temperature(T_(g))was−80.5℃and thermal decomposition peak temperature was 267.59℃.While mechanical sensitivities showed that the impact sensitivity was measured as H_(50)=125.9 cm,the friction sensitivity was 0.Those results indicated that DNPTFP had good thermal properties as well as insensitive mechanical sensitivities.Besides,as miscibility test,viscosity and Tg measurements turned out,DNPTFP had good miscibility with glycide azide polymer(GAP),and demonstrated notable adjust ability on the viscosity and Tg of GAP.Moreover,along with higher mixing ratio of DNPTFP,lower fluidity activation energy and higher plasticizing efficiency was achieved.Therefore,DNPTFP exhibited excellent plasticizing effect on GAP,which indicating good potential application in GAP based explosives and propellant.

关 键 词：含能增塑剂 2 2-偕二硝基丙基三氟丙酸酯 酯化反应 玻璃化转变温度 黏度 

分 类 号：O623.6[理学—有机化学]