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

摘要

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（NaOH）＝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.