1,3,5-三硝基-六氢化-1,3,5-三嗪-2(1H)-酮(Keto-RDX)新法合成、晶体结构和热性能研究

A Novel Synthetic Route, Crystal Structure and Thermal Behaviors for 1,3,5-Trinitro-hexahydro-1,3,5-triazin-2(1H)-one (Keto-RDX)

研究了1,3,5-三硝基-六氢化-1,3,5-三嗪-2(1H)-酮(Keto-RDX)的合成新方法,以乌洛托品和硝基胍为原料,通过Mannich反应得到2-硝亚胺基-六氢化-1,3,5-三嗪盐酸盐(NIHT·HCl),用HNO3/AC2O硝化可得Keto-RDX,并采用核磁共振、红外、质谱以及元素分析等进行了结构表征.培养了Keto-RDX单晶,晶体结构解析表明:晶体属于正交晶系,空间群Pnma,晶胞参数a=1.0057(17)nm,b=1.3483(2)nm,c=0.5982(10)nm,V=0.8112(2)nm3,Z=4,Dc=1.933 g/cm3,μ=0.188 mm-1,F(000)=480.差示扫描量热(DSC)法和热失重(TG/DTG)法分析表明,Keto-RDX分解峰温为211.4℃(DSC),在185.00～202.79℃为固相分解阶段,峰温为198.61℃,质量损失为21.45%,在202.79～230.00℃为液相分解阶段,质量损失为77.83%,峰温为213.78℃,热稳定性较RDX差.

1,3,5-Trinitro-hexahydro-1,3,5-triazin-2（1H）-one（Keto-RDX） was synthesized by a novel route of Mannich reac-were a=1.0057（17） nm,b=1.3483（2） nm,c=0.5982（10） nm,V=0.8112（2） nm3,Z=4,Dc=1.933 g/cm3,μ=0.188 mm-1,tion and nitration reaction for nitroguanidine and urotropine,which were used as starting materials,with a yield of 72.0% and a purity of 98.5%.The structures of Keto-RDX were characterized by 1H NMR,13C NMR,FT-IR,MS techniques and elemen-tal analysis.It was found that Keto-RDX belongs to orthorhombic system with space group Pnma,and the crystal parameters F（000）=480.The thermal decomposition behavior of Keto-RDX was studied by DSC and TG/DTG techniques.The results showed that there was a single sharp exothermic decomposition with peak maximum at 211.4 ℃（DSC）,and the thermal decomposition processes can be divided into two stages.