1-氨基-3-甲基-1，2，3-三唑硝酸盐的合成及性能研究
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摘要
TNT由于渗油、高蒸汽压等缺点,人们一直在寻找它的替代物。1-氨基-3-甲基-1,2,3-三唑硝酸盐(1-AMTN)是一种含能离子盐,它具有适当的熔点,比TNT更好的爆炸性能,可以替代TNT作为熔铸炸药的高能液相载体。
本课题以乙二醛、水合肼为起始原料,经加成-消除、环化、甲基化、置换四步反应得到1-AMTN,总收率68.1%。优化了加成-消除反应、环化反应和甲基化反应的的工艺条件。实验发现：(1)以甲醇作溶剂,n(水合肼)：n(乙二醛)=3：1,n(乙酸)：n(乙二醛)=0.3：100,反应温度为70℃,反应时间为5h时,加成-消除反应收率最高,可达到90.7%；(2)以乙腈作溶剂,n(二氧化锰)：n(乙二腙)=2.8：1,反应温度为20℃,反应时间为2.5h时,环化反应收率最高,可达到87.5%；(3)溶剂为乙腈,n(1-氨基-1,2,3-三唑)：n(碘甲烷)=1：6,反应温度为20℃,反应时间为12h,甲基化收率最高,可达到90.1%。
改进合成工艺,将环化后的产物不经过纯化直接用于下一步反应,避免了重结晶对产物的损失,并对改进后的环化和甲基化工艺进行了优化：溶剂为乙腈,反应温度20℃,n(乙二腙)：n(二氧化锰)：n(碘甲烷)=0.028：0.078：0.14,环化时间为2.5h,甲基化时间为12h,环化甲基化总收率86.7%,1-AMTN总收率提高到74.9%。
通过元素分析、核磁、红外、质谱等分析手段对1-AMTN进行了结构表征；对活性二氧化锰进行了回收利用并探究了其作用机理；采用差示扫描量热法(DSC)测定了1-AMTN的熔点为88℃,分解温度为273℃；测定了1-AMTN的爆轰性能：撞击感度为16%,摩擦感度为24%,爆速为7780m/s,爆压为21.2GPa。
Researchers are searching for advanced replacements for TNT for its disadvantage such as oil seepage and high vapor pressure. 1-amino-3-methyl-1,2,3-triazolium nitrate(1-AMTN) is one kind of energetic ionic liquids, It has appropriate melt point and superior explosive performance over TNT, so it can be used as high-energy liquid carrier in melt castable explosives。
1-AMTN was synthesized using glyoxal and hydrazine hydrate as starting materials in four steps including addition-elimination, cyclization, methylation and replacement reaction, the overall yield is 68.1%(based on glyoxal). The reaction conditions of addition-elimination, cyclization and methylation were optimized. The optimal reaction conditions were confirmed: (1). Medium methanol, the ratio of aqueous hydrazine and glyoxal 3:1, the ratio of acetic acid and glyoxal 0.3:100, reaction temperature 70℃, reaction time 5h, to the yield 90.7%; (2) medium acetonitrile, the ratio of activated manganese dioxide and glyoxal bishydrazone 2.8:1, reaction temperature 20℃, reaction time 2.5h, to the yield 87.5%; (3) medium acetonitrile, the ratio of 1-amino-1,2,3-triazole and methyl iodide 1:6, reaction temperature 20℃, reaction time 12h, to the yield 90.1%.
The process conditions of cyclization and methylation were improved and optimized: medium acetonitrile, the ratio of glyoxal and methyl iodide 1:5, reaction temperature 20℃, cyclization time 2.5h, methylation time 12h, the yield of cyclization and methylation was 86.7%, the overall yield of 1-AMTN was improved to 74.9%, which indicates that it is a better method than the method reported.
The structure of product was confirmed by elemental analysis, IR, MS and NMR. Actived manganese oxide was recycled and its mechanism was discussed. The melt point and decomposition onset temperature are confirmed by DSC. The explosive performances were measured:impact sensitivity 16%, friction sensitivity 24%, explosive velocity 7780m/s, C-J pressure 21.2GPa.
本课题以乙二醛、水合肼为起始原料,经加成-消除、环化、甲基化、置换四步反应得到1-AMTN,总收率68.1%。优化了加成-消除反应、环化反应和甲基化反应的的工艺条件。实验发现：(1)以甲醇作溶剂,n(水合肼)：n(乙二醛)=3：1,n(乙酸)：n(乙二醛)=0.3：100,反应温度为70℃,反应时间为5h时,加成-消除反应收率最高,可达到90.7%；(2)以乙腈作溶剂,n(二氧化锰)：n(乙二腙)=2.8：1,反应温度为20℃,反应时间为2.5h时,环化反应收率最高,可达到87.5%；(3)溶剂为乙腈,n(1-氨基-1,2,3-三唑)：n(碘甲烷)=1：6,反应温度为20℃,反应时间为12h,甲基化收率最高,可达到90.1%。
改进合成工艺,将环化后的产物不经过纯化直接用于下一步反应,避免了重结晶对产物的损失,并对改进后的环化和甲基化工艺进行了优化：溶剂为乙腈,反应温度20℃,n(乙二腙)：n(二氧化锰)：n(碘甲烷)=0.028：0.078：0.14,环化时间为2.5h,甲基化时间为12h,环化甲基化总收率86.7%,1-AMTN总收率提高到74.9%。
通过元素分析、核磁、红外、质谱等分析手段对1-AMTN进行了结构表征；对活性二氧化锰进行了回收利用并探究了其作用机理；采用差示扫描量热法(DSC)测定了1-AMTN的熔点为88℃,分解温度为273℃；测定了1-AMTN的爆轰性能：撞击感度为16%,摩擦感度为24%,爆速为7780m/s,爆压为21.2GPa。
Researchers are searching for advanced replacements for TNT for its disadvantage such as oil seepage and high vapor pressure. 1-amino-3-methyl-1,2,3-triazolium nitrate(1-AMTN) is one kind of energetic ionic liquids, It has appropriate melt point and superior explosive performance over TNT, so it can be used as high-energy liquid carrier in melt castable explosives。
1-AMTN was synthesized using glyoxal and hydrazine hydrate as starting materials in four steps including addition-elimination, cyclization, methylation and replacement reaction, the overall yield is 68.1%(based on glyoxal). The reaction conditions of addition-elimination, cyclization and methylation were optimized. The optimal reaction conditions were confirmed: (1). Medium methanol, the ratio of aqueous hydrazine and glyoxal 3:1, the ratio of acetic acid and glyoxal 0.3:100, reaction temperature 70℃, reaction time 5h, to the yield 90.7%; (2) medium acetonitrile, the ratio of activated manganese dioxide and glyoxal bishydrazone 2.8:1, reaction temperature 20℃, reaction time 2.5h, to the yield 87.5%; (3) medium acetonitrile, the ratio of 1-amino-1,2,3-triazole and methyl iodide 1:6, reaction temperature 20℃, reaction time 12h, to the yield 90.1%.
The process conditions of cyclization and methylation were improved and optimized: medium acetonitrile, the ratio of glyoxal and methyl iodide 1:5, reaction temperature 20℃, cyclization time 2.5h, methylation time 12h, the yield of cyclization and methylation was 86.7%, the overall yield of 1-AMTN was improved to 74.9%, which indicates that it is a better method than the method reported.
The structure of product was confirmed by elemental analysis, IR, MS and NMR. Actived manganese oxide was recycled and its mechanism was discussed. The melt point and decomposition onset temperature are confirmed by DSC. The explosive performances were measured:impact sensitivity 16%, friction sensitivity 24%, explosive velocity 7780m/s, C-J pressure 21.2GPa.
引文
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[9]余咸宽,孙宽德,白刚等.添加六硝基芪改善梯恩梯为基的熔铸炸药铸药晶粒的研究[C].中国工程院化工、冶金与材料工程学部第五届学术会议,2005
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[11]赵省向,张亦安,王晓峰等.EAK基熔铸分子间炸药的能量和撞击感度[J].火炸药学报,2004,27(3)：29-31
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