含能材料
含能材料
함능재료
ENERGETIC MATERIALS
2014年
6期
744-747
,共4页
赵廷兴%田均均%李磊%范桂娟%张光全%李鸿波%黄明
趙廷興%田均均%李磊%範桂娟%張光全%李鴻波%黃明
조정흥%전균균%리뢰%범계연%장광전%리홍파%황명
有机化学%合成%5,5′-联四唑-1,1′-二氧二羟铵(TKX-50)
有機化學%閤成%5,5′-聯四唑-1,1′-二氧二羥銨(TKX-50)
유궤화학%합성%5,5′-련사서-1,1′-이양이간안(TKX-50)
organic chemistry%synthesis%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(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%。
為穫得綠色低感高能炸藥,研究瞭5,5′-聯四唑-1,1′-二氧二羥銨( TKX-50)的50剋量級製備方法。以乙二醛為起始原料,通過肟化、氯代、疊氮化、環閤製得瞭關鍵中間體5,5′-聯四唑-1,1′-二羥基二水閤物(1,1′-BTO),1,1′-BTO與羥胺水溶液成鹽直接製備齣目標物TKX-50,產品經1H NMR,IR,MS,DSC和元素分析確證結構。重點攷察瞭由1,1′-BTO製備TKX-50反應中投料比、時間及溫度對收率的影響,確定瞭適宜的工藝條件:投料摩爾比 n(1,1′-BTO)∶ n(NH2OH·HCl)∶ n(NaOH)=1∶2.2∶2.2,反應時間1 h,溫度80℃時,單步反應收率80.1%。閤成路線總收率為41.5%。
위획득록색저감고능작약,연구료5,5′-련사서-1,1′-이양이간안( TKX-50)적50극량급제비방법。이을이철위기시원료,통과우화、록대、첩담화、배합제득료관건중간체5,5′-련사서-1,1′-이간기이수합물(1,1′-BTO),1,1′-BTO여간알수용액성염직접제비출목표물TKX-50,산품경1H NMR,IR,MS,DSC화원소분석학증결구。중점고찰료유1,1′-BTO제비TKX-50반응중투료비、시간급온도대수솔적영향,학정료괄의적공예조건:투료마이비 n(1,1′-BTO)∶ n(NH2OH·HCl)∶ n(NaOH)=1∶2.2∶2.2,반응시간1 h,온도80℃시,단보반응수솔80.1%。합성로선총수솔위41.5%。
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.