Modification And Polymerization Of 4,4'-azo-1,2,4-triazole

Azole compounds because of its unique structure having a wide range of physiological,pharmacological activities,and having a high nitrogen content,high heat generation,high-density,structural stability,environmentally friendly and easy to modify,etc.Therefore,in medicine,pesticides and energetic materials and other fields with a wide range of research and application.Azole polymers are also used in biomedical materials,optical materials,porous materials,solar cell materials,energetic materials and other fields because of their biological activity,conjugated structure and high energy and high stability.4,4'-Azo-1,2,4-triazole is an ideal energetic skeleton due to its high heat of formation(878kJ·mol^-1)and high stability?decomposition temperature of 313°C?.And its polymer has potential application value in biological antibacterial materials,nonlinear optical materials and energetic binder.Therefore,modification and polymerization of 4,4'-azo-1,2,4-triazole are of great significance for the development of new energy-containing materials and new functional polymer materials.In this paper,the modification and polymerization of 4,4'-azo-1,2,4-triazole were studied,various derivatives and polymers of 4,4'-azo-1,2,4-triazole were synthesized.The structure and properties of products were characterized by IR,MS,¹H-NMR,¹³C-NMR,TG-DSC,X-ray single crystal diffraction etc.Synthesis of polychlorinated azo-1,2,4-triazole,and the 3,5-dichloro-1,2,4-triazole is obtained by the decomposed of 3,3',5,5'-tetrachloro-4,4'-azo-1,2,4-triazole.The method is mild and easy to operate,and the chlorinated reagent sodium dichloroisocyanurate is inexpensive and non-toxic.The aminolysis and hydrolysis of azo-1,2,4-triazole were studied.3-Chloro-3'-amino-azo-1,2,4-triazole was obtained by dichloro-azo-triazole reacted with aqueous ammonia.Dichloro-and tetrachloro-4,4'-azo-1,2,4-triazole was reacted with aqueous sodium hydroxide solution,respectively,to give 3,3'-dihydroxy-4,4'-azo-1,2,4-triazole and 3,3'-dichloro-4,4'-azo-1,2,4-triazolone sodium salt,respectively.The properties of several azo-triazole derivatives were predicted by theoretical calculation.The results showed that their derivatives had high energy and stability.Six polymers were prepared by the polymerization of 3,3'-diamino-4,4'-azo-1,2,4-triazole and 3,3'-dihydroxy-4,4'-azo-1,2,4-triazole with?HMDI?,isophorone diisocyanate?IPDI?and hexamethylene diisocyanate?HDI?,respectivly.Which were the first time the polymer with azo-triazole structural units in the main chain were obtained.Their molecular weight were between 2000 and 7000 which measured by MALDI-TOF.And TG-DSC showed they have good thermal stability.Sixteen compounds were synthesized and two single crystal structures were obtained.Eleven of them were not reported,including six polymers.