5,5'-联四唑-1,1'-二氧二羟铵(TKX-50)50克量级制备放大工艺

Up-sizing 50 Grams-scale Synthesis Technology of Dihydroxylammonium 5,5'-Bistetrazole-l,1'-diolate(TKX-50)

为获得绿色低感高能炸药,研究了5,5'-联四唑-1,1'-二氧二羟铵(TKX-50)的50克量级制备方法。以乙二醛为起始原料,通过肟化、氯代、叠氮化、环合制得了关键中间体5,5'-联四唑-1,1'-二羟基二水合物(1,1'-BTO),1,1'-BTO与羟胺水溶液成盐直接制备出目标物TKX-50,产品经1H NMR,IR,MS,DSC和元素分析确证结构。重点考察了由1,1'-BTO制备TKX-50反应中投料比、时间及温度对收率的影响,确定了适宜的工艺条件:投料摩尔比n(1,1'-BTO)∶n(NH2OH·HCl)∶n(Na OH)=1∶2.2∶2.2,反应时间1 h,温度80℃时,单步反应收率80.1%。合成路线总收率为41.5%。

In order to obtain green and insensitive high energy explosives,50 grams-scale synthetic method of dihydroxylammonium 5,5′-bistetrazole-1,1′-diolate（TKX-50）was investigated. The key intermediate of 5,5′-bistetrazole-1,1′-diol dihydrate（1,1′-BTO）was synthesized through oximation,chlorination,azidation and cyclization from glyoxal. TKX-50 was successfully obtained from the reaction of 1,1-BTD with hydroxylamine aqueous solution. The product was characterized by 1H NMR,IR,MS,DSC and element analysis. In the preparation process of TKX-50 from 1,1′-BTO,the influence of molar ratio of reactants,reaction time and temperature on the yield of TKX-50 were studied. The optimal conditions of the process were determined：when the reaction was operated at 80 ℃ for 1h with the molar ratio of n（1,1′-BTO）∶ n（NH2OH·HCl）∶ n（NaOH）= 1 ∶ 2.2 ∶ 2.2. The yield could achieve in 80 . 1%. The total yield of the synthetic route is 41 . 5 %. The technology is valuable for the preparation of TKX-50 in large scale.