CN116041340A - 3-氨基-4-（4-氨基-5-肼基-1,2,4-三唑-3-基）呋咱及其含能离子盐 - Google Patents
3-氨基-4-（4-氨基-5-肼基-1,2,4-三唑-3-基）呋咱及其含能离子盐 Download PDFInfo
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Abstract
本发明公开了一种3‑氨基‑4‑（4‑氨基‑5‑肼基‑1,2,4‑三唑‑3‑基）呋咱及其含能离子盐，属于有机含能材料领域。合成过程如下：（1）三氨基胍盐酸盐与3‑氨基‑4‑羧基‑呋咱在磷酸和五氧化二磷的酸性体系中反应制得3‑氨基‑4‑（4‑氨基‑5‑肼基‑1,2,4‑三唑‑3‑基）呋咱；（2）选择含阴离子的化合物，经成盐反应制得目标含能离子盐。本发明中合成的化合物及其含能离子盐均具有高含氮量、正生成焓及良好的爆轰性能，且本发明所述的合成方法工艺安全合理、反应时间短、收率高。
Description
技术领域
本发明涉及3-氨基-4-(4-氨基-5-肼基-1,2,4-三唑-3-基)呋咱及其离子盐，属于有机含能材料技术领域。
背景技术
含能材料是一类含有爆炸性基团或含有氧化剂和可燃物、能独立进行化学反应并输出能量的化合物或混合物，是军用炸药、发射药和火箭推进剂配方的重要组成部分。含能材料的能量水平直接决定武器装备的毁伤、打击能力。含能材料的能量水平与安全性存在着固有的矛盾：含能材料的能量水平越高，其安全性一般就会随之降低。
为满足含能材料对能量和安全的双重要求，开发研究新型高能低感含能材料成为目前含能材料领域的重要发展方向。顿感含能化合物指灵敏度较低，一般指撞击感度大于40J，摩擦感都大于360N的含能化合物。在过去的几十年里，研究发现，吡唑和咪唑很稳定，但能量水平太低，爆轰速度只能维持在7000m/s左右。为提高含能材料的爆轰性能，通过提高氮含量发明出了多种全氮类化合物。通过修饰连接基团，多氨基高氮化合物在满足高爆速高爆压的同时，含能材料的稳定性却很难保证，热稳定差、感度高，在实际应用方面存在较大问题。
目前研究发现，三唑、四唑是较好的可以平衡爆轰性能和稳定性的含能材料母体，对含能材料领域是十分有价值的研究。为了平衡含能材料的感度并且提高其爆轰性能，氮杂环含能材料应运而生。近年的研究发现，在分子结构中引入“–NH2、–NHNH2”基团能够形成分子内和分子间氢键，可以有效降低含能材料的感度并在一定程度上保持了较好的爆轰性能。因此，设计多–NH2取代的唑类含能材料具有优良的能量与安全性能，可更好地协调含能材料能量与感度的关系。
因此，以1，2，4-三唑连接呋咱的3-氨基-4-(4-氨基-5-肼基-1,2,4-三唑-3-基)呋咱及其离子盐是既具有较好的爆轰性能，又具有较低的撞击感度及摩擦感度的氮杂环含能材料。该化合物在安全性和能量之间取得平衡，同时呋咱基团提高了化合物氧平衡性，为含能材料领域的设计提供了新思路。
发明内容
本发明的目的在于提供3-氨基-4-(4-氨基-5-肼基-1,2,4-三唑-3-基)呋咱及其离子盐的合成方法。
本发明的目的是通过以下技术方案实现的。
本发明的3-氨基-4-(4-氨基-5-肼基-1,2,4-三唑-3-基)呋咱，其通式为：
其含能离子盐的通式为：
本发明所述含能离子盐的合成方法，包括：
步骤1)将化合物1与三氨基胍盐酸盐在磷酸的酸性环境下，经过脱水反应，由过量五氧化二磷作为吸水剂，制得化合物2的步骤，
步骤2)将化合物2与阴离子溶液反应制得离子盐的步骤；
作为本发明的一个优选实施例，步骤(1)中，化合物1与三氨基胍盐酸盐的摩尔比为1：1.2-1.6；脱水反应在酸性环境下进行，所述的酸性条件为磷酸；脱水反应的吸水剂采用过量的五氧化二磷；脱水反应温度为120℃，反应时间为6-8h。
作为本发明的一个优选实施例，步骤(2)中，反应体系的反应溶剂为水，阴离子溶液为盐酸、硝酸、高氯酸、5-硝基四唑、3-氨基-4-四唑呋咱、3,5-二硝基吡唑、2,4,6-三硝基-1,3,5-苯三酚、苦味酸、三硝基甲烷或二硝酰胺中任意一种，化合物2与阴离子溶液的摩尔比为1:1-1:1.5。
与现有技术相比，本发明的显著优点是：
1)本发明通过构建多氨基唑类化合物，在保证唑类化合物高爆轰性能的同时，提高了化合物的稳定性。
2)本发明得到一系列含能离子盐，经测试密度介于1.559-1.87g·cm-1之间，生成焓介于-17.59-929.57kJ·mol-1，是良好的高能量顿感含能材料。
3)本发明涉及的合成方法工艺安全合理、反应条件温和、收率较高、生产成本低、基本无三废、对环境友好。
附图说明
图1为本发明化合物4的晶体结构图。
图2为本发明化合物9的晶体结构图。
图3为本发明化合物4的核磁图。
图4为本发明化合物5的核磁图。
图5为本发明化合物9的核磁图。
图6为本发明化合物4的红外图。
图7为本发明化合物5的红外图。
图8为本发明化合物9的红外图。
图9为本发明化合物4的DSC图。
图10为本发明化合物9的DSC图。
具体实施方式
下面结合实例对本发明做进一步说明，但本发明的保护范围并不限于此。
本发明设计并合成了以三唑、呋咱为骨架，氨基为取代基团的3-氨基-4-(4-氨基-5-肼基-1,2,4-三唑-3-基)呋咱及其含能离子盐，具有高生成焓、高爆速以及良好的稳定性，可用于有机含能材料领域。
本发明所述目标化合物的总合成路线如下：
本发明所述的合成方法，其具体步骤如下：
步骤1)化合物2的制备：取3-氨基-4-羧基-呋咱(根据现有文献自制)、三氨基胍盐酸盐(根据现有文献自制)与五氧化二磷于研钵中混合均匀，倒入磷酸中，反应6-8h。反应结束后，倒入120ml冰水中冰淬，并用浓氢氧化钠调至pH＝8，制得化合物2。
步骤(2)化合物3-12的制备：将化合物2分别与盐酸、硝酸、高氯酸、5-硝基四唑、3-氨基-4-四唑呋咱、3,5-二硝基吡唑、2,4,6-三硝基-1,3,5-苯三酚、苦味酸、三硝基甲烷或二硝酰胺溶液混合反应，反应结束，旋蒸即可得化合物3-12。
实施例1
化合物2的制备：室温下，五氧化二磷(10g，75mmol)溶解于磷酸(30g，25mmol)中，溶液加热至50℃，将3-氨基-4-羧基-呋咱(3.87g，30mmol)和三氨基胍盐酸盐(7g，50mmol)的混合粉末分批加入到溶液中，升温至120℃反应6-8h，反应结束后冷却至室温，将所得油状反应液倒入120ml冰水混合物中，用浓氢氧化钠溶液调至pH＝8，过滤，水洗得2(3.53g，20.39mmol)，产率59.8％。
实施例2
化合物3的制备：将0.197g(1mmol)化合物2分散于10mL水中，然后向水中滴加5mL2mol/L的稀盐酸，滴加完毕后升温至80℃，搅拌0.5h，过滤除去不溶物，旋蒸得到化合物3，产率85％。经真密度仪测得，其密度为1.559g/cm3；经采用标准BAM落锤和BAM摩擦试验机测试了冲击和摩擦灵敏度，其冲击敏感度>40J，摩擦敏感度>360N；经Gaussian 09software32计算得，其生成焓为352.47kJ·mol-1；爆轰特性由Explo5(version 6.02)根据计算出的生成热和室温下的测量密度估算，爆速为5936m·s-1，爆压为14.3GPa。
实施例3
化合物4的制备:将0.197g(1mmol)化合物2分散于10mL水中，然后向水中滴加5mL2mol/L的稀硝酸，滴加完毕后升温至80℃，搅拌0.5h，过滤除去不溶物，旋蒸得到化合物4，产率86％。其晶体结构见图1，核磁见图3，红外见图6，DSC见图9；经真密度仪测得，其密度为1.727g/cm3；经采用标准BAM落锤和BAM摩擦试验机测试了冲击和摩擦灵敏度，其冲击敏感度>40J，摩擦敏感度>360N；经Gaussian 09 software32计算得，其生成焓为590.77kJ·mol-1；爆轰特性由Explo5(version 6.02)根据计算出的生成热和室温下的测量密度估算，爆速为8698m·s-1，爆压为29.49GPa。
实施例4
化合物5的制备：将0.197g(1mmol)化合物2分散于10mL水中，然后向水中滴加5mL2mol/L的高氯酸，滴加完毕后升温至80℃，搅拌0.5h，过滤除去不溶物，旋蒸反应液得到化合物5，产率88％。其核磁见图4，红外见图7。经真密度仪测得，其密度为1.799g/cm3；经采用标准BAM落锤和BAM摩擦试验机测试了冲击和摩擦灵敏度，其冲击敏感度>40J，摩擦敏感度>360N；经Gaussian 09 software32计算得，其生成焓为670.59kJ·mol-1；爆轰特性由Explo5(version 6.02)根据计算出的生成热和室温下的测量密度估算，爆速为8072m·s-1，爆压为28.90GPa。
实施例5
化合物6的制备，将0.63g(2.5mmol)化合物3溶于20mL水中，然后向水中滴加3.0g的5-硝基四唑银盐在水中的悬浊溶液，滴毕在常温下避光搅拌1h，反应结束后过滤、水洗，用旋转蒸发的方法除去滤液中的水得到化合物6，产率为83％。经真密度仪测得，其密度为1.722g/cm3；经Gaussian 09 software32计算得，其生成焓为741.83kJ·mol-1；爆轰特性由Explo5(version 6.02)根据计算出的生成热和室温下的测量密度估算，爆速为7773m·s-1，爆压为26.1GPa。
实施例6
化合物7的制备：将化合物2(0.197g，1mmol)分散于10mL水中，再加入3-氨基-4-四唑呋咱(0.153g，1mmol)，滴入2mL盐酸(1M)，加热至80℃，使体系变为澄清溶液，搅拌0.5h，缓慢冷却至室温，有固体析出，过滤，干燥，得到化合物7，产率81％。经真密度仪测得，其密度为1.701g/cm3；经Gaussian 09 software32计算得，其生成焓为929.57kJ·mol-1；爆轰特性由Explo5(version 6.02)根据计算出的生成热和室温下的测量密度估算，爆速为7404m·s-1，爆压为23.5GPa。
实施例7
化合物8的制备：将化合物2(0.197g，1mmol)分散于10mL水中，再加入3,5-二硝基吡唑(0.158g，1mmol)，滴入2mL盐酸(1M)，加热至80℃，使体系变为澄清溶液，搅拌0.5h，缓慢冷却至室温，有固体析出，过滤，干燥，得到化合物8，产率80％。经真密度仪测得，其密度为1.749g/cm3；经Gaussian 09 software32计算得，其生成焓为603.3kJ·mol-1；爆轰特性由Explo5(version 6.02)根据计算出的生成热和室温下的测量密度估算，爆速为7704m·s-1，爆压为25.9GPa。
实施例8
化合物9的制备：将化合物2(0.197g，1mmol)分散于10mL水中，再加入2,4,6-三硝基-1,3,5-苯三酚(0.261g，1mmol)，滴入2mL盐酸(1M)，加热至80℃，使体系变为澄清溶液，搅拌0.5h，缓慢冷却至室温，有固体析出，过滤，干燥，得到化合物9，产率80％。其晶体结构见图2，核磁见图5，红外见图8，DSC见图10。经真密度仪测得，其密度为1.862g/cm3；经采用标准BAM落锤和BAM摩擦试验机测试了冲击和摩擦灵敏度，其冲击敏感度>40J，摩擦敏感度>360N；经Gaussian 09 software32计算得，其生成焓为-19.3kJ·mol-1；爆轰特性由Explo5(version 6.02)根据计算出的生成热和室温下的测量密度估算，爆速为8064m·s-1，爆压为26.42GPa。
实施例9
化合物10的制备：将化合物2(0.197g，1mmol)分散于10mL水中，再加入苦味酸(0.229g，1mmol)，加热至80℃，使体系变为澄清溶液，搅拌0.5h，缓慢冷却至室温，有固体析出，过滤，干燥，得到化合物10，产率78％。经真密度仪测得，其密度为1.798g/cm3；经Gaussian 09 software32计算得，其生成焓为317.88kJ·mol-1；爆轰特性由Explo5(version 6.02)根据计算出的生成热和室温下的测量密度估算，爆速为7642m·s-1，爆压为25.9GPa。
实施例10
化合物11的制备：将化合物2(0.197g，1mmol)分散于10mL水中，再加入三硝基甲烷(0.151g，1mmol)，加热至80℃，使体系变为澄清溶液，搅拌0.5h，缓慢冷却至室温，有固体析出，过滤，干燥，得到化合物11，产率78％。经真密度仪测得，其密度为1.816g/cm3；经Gaussian 09 software32计算得，其生成焓为437.76kJ·mol-1；爆轰特性由Explo5(version 6.02)根据计算出的生成热和室温下的测量密度估算，爆速为8520m·s-1，爆压为32.41GPa。
实施例11
化合物12的制备：将化合物2(0.197g，1mmol)分散于10mL水中，再加入二硝酰胺铵(0.124g，1mmol)，滴入2mL盐酸(1M)，加热至80℃，使体系变为澄清溶液，搅拌0.5h，缓慢冷却至室温，有固体析出，过滤，干燥，得到化合物12，产率78％。经真密度仪测得，其密度为1.755g/cm3；经Gaussian 09 software32计算得，其生成焓为511.49kJ·mol-1；爆轰特性由Explo5(version 6.02)根据计算出的生成热和室温下的测量密度估算，爆速为8288m·s-1，爆压为30.0GPa。
Claims (10)
1.一种含能化合物，其特征在于，命名为3-氨基-4-(4-氨基-5-肼基-1,2,4-三唑-3-基)呋咱，其通式为：
2.一种含能离子盐，其特征在于，其通式为：
3.如权利要求1所述的含能化合物的合成方法，其特征在于，包括：
将化合物1与三氨基胍盐酸盐在磷酸的酸性环境下，经过脱水反应，由过量五氧化二磷作为吸水剂，制得目标产物化合物2的步骤，
4.如权利要求3所述的方法，其特征在于，化合物1与三氨基胍盐酸盐的摩尔比为1：1.2-1.6。
5.如权利要求3所述的方法，其特征在于，脱水反应在酸性环境下进行，所述的酸性条件为磷酸。
6.如权利要求3所述的方法，其特征在于，脱水反应的吸水剂采用过量的五氧化二磷。
7.如权利要求3所述的方法，其特征在于，脱水反应温度为120℃，反应时间为6-8h。
8.如权利要求2所述的含能离子盐的合成方法，其特征在于，包括：将如权利要求1所述的含能化合物2与阴离子溶液反应制得离子盐的步骤；
9.如权利要求8所述的方法，其特征在于，反应体系的反应溶剂为水，阴离子溶液为盐酸、硝酸、高氯酸、5-硝基四唑、3-氨基-4-四唑呋咱、3,5-二硝基吡唑、2,4,6-三硝基-1,3,5-苯三酚、苦味酸、三硝基甲烷或二硝酰胺中任意一种。
10.如权利要求8所述的方法，其特征在于，含能化合物2与阴离子溶液的摩尔比为1:1-1:1.5。
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