新型多氮化合物1,1'-偶氮-1,2,3-三唑的合成与性能研究

Synthesis and Performance of A Novel Poly-nitrogen Compound 1,1'-Azobis-1,2,3-triazole

以1-氨基-1,2,3-三唑(1)为原料,经二氯异氰尿酸钠(SDCI)氧化偶联合成了具有稳定N8结构(8个氮原子直接相连)和光致变色特性的新型多氮化合物1,1'-偶氮-1,2,3-三唑(2),通过IR,Raman,1H NMR,13C NMR,MS,元素分析等手段对其进行了表征;分离出了偶合反应副产物1H-1,2,3-三唑(3);推测了2的质谱裂解机理.在DFT-B3LYP/6-31G*水平下对2的结构进行了计算,理论计算结合实测数据比较表明:单环中引入偶氮键能够有效增加多氮化合物的密度和生成热,与3相比,2密度增加37.6%,生成热增加48.8%;在不同类型的偶氮三唑化合物中,直接相连的氮原子数目越多含能性质越突出,与3,3'-偶氮-1,2,3-三唑(4)相比,2密度增加5.6%,生成热增加51.0%.

1,1＇-Azobis-1,2,3-triazole（2）,a novel poly-nirogen compound with stable N8 structure（eight directly linked nitrogen atoms） and photochromism,has been synthesized from 1-amino-1,2,3-triazole（1） by the oxidative coupling reaction（sodium dichloroisocyanurate（SDCI） as the oxidant） and its structure were characterized by IR,Raman,1H NMR,13C NMR,MS and elementary analysis techniques.1H-1,2,3-triazole（3） was separated as the by-product and the decomposed mechanism of 2 were presumed.The structure of 2 was also estimated by the density functional theory（DFT） method based on B3LYP/6-31G＊ basis set.By the theoretical results and experimental data,introduction of azo group into single-ring poly-nitrogen com-pounds can efficiently increase their density and heat of formation,by comparison with the performance of 3,the density and heat of formation of 2 increase 37.6% and 48.8% respectively;also the performance of different types of azobis-triazoles was compared,and the results indicated that the larger the number of di-rectly linked nitrogen atoms,the more excellent it＇s performance is,e.g.the density and the heat of forma-tion of 2 increased by 5.6% and 51.0% respectively compared with 3,3＇-azobis-1,2,3-triazole（4）.