CN108840833B - 二(1,5-硝胺基四唑)-四水合铜化钾化合物 - Google Patents
二(1,5-硝胺基四唑)-四水合铜化钾化合物 Download PDFInfo
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- VDNXILQBKLFION-UHFFFAOYSA-N [K].[Cu] Chemical compound [K].[Cu] VDNXILQBKLFION-UHFFFAOYSA-N 0.000 title claims abstract description 18
- ULRPISSMEBPJLN-UHFFFAOYSA-N 2h-tetrazol-5-amine Chemical compound NC1=NN=NN1 ULRPISSMEBPJLN-UHFFFAOYSA-N 0.000 claims description 2
- 230000037452 priming Effects 0.000 abstract description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 12
- 230000036571 hydration Effects 0.000 description 12
- 238000006703 hydration reaction Methods 0.000 description 12
- YWVHJAFUGSRCQB-UHFFFAOYSA-N [N+](=O)([O-])N1N(NN=C1[N+](=O)[O-])N Chemical compound [N+](=O)([O-])N1N(NN=C1[N+](=O)[O-])N YWVHJAFUGSRCQB-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000004880 explosion Methods 0.000 description 8
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 7
- 239000001103 potassium chloride Substances 0.000 description 7
- 235000011164 potassium chloride Nutrition 0.000 description 7
- 238000001914 filtration Methods 0.000 description 6
- ZGZLYKUHYXFIIO-UHFFFAOYSA-N 5-nitro-2h-tetrazole Chemical compound [O-][N+](=O)C=1N=NNN=1 ZGZLYKUHYXFIIO-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical group 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 4
- 238000005474 detonation Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 235000000396 iron Nutrition 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 238000004566 IR spectroscopy Methods 0.000 description 2
- BSPUVYFGURDFHE-UHFFFAOYSA-N Nitramine Natural products CC1C(O)CCC2CCCNC12 BSPUVYFGURDFHE-UHFFFAOYSA-N 0.000 description 2
- 150000001540 azides Chemical class 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- POCJOGNVFHPZNS-UHFFFAOYSA-N isonitramine Natural products OC1CCCCC11CNCCC1 POCJOGNVFHPZNS-UHFFFAOYSA-N 0.000 description 2
- WETZJIOEDGMBMA-UHFFFAOYSA-L lead styphnate Chemical compound [Pb+2].[O-]C1=C([N+]([O-])=O)C=C([N+]([O-])=O)C([O-])=C1[N+]([O-])=O WETZJIOEDGMBMA-UHFFFAOYSA-L 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 125000003831 tetrazolyl group Chemical group 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- MWCRFDZMVUBRKR-UHFFFAOYSA-N [N].C1=NN=NN1 Chemical group [N].C1=NN=NN1 MWCRFDZMVUBRKR-UHFFFAOYSA-N 0.000 description 1
- OOIOHEBTXPTBBE-UHFFFAOYSA-N [Na].[Fe] Chemical compound [Na].[Fe] OOIOHEBTXPTBBE-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005649 metathesis reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 150000003388 sodium compounds Chemical class 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D257/00—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms
- C07D257/02—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D257/04—Five-membered rings
- C07D257/06—Five-membered rings with nitrogen atoms directly attached to the ring carbon atom
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B25/00—Compositions containing a nitrated organic compound
- C06B25/34—Compositions containing a nitrated organic compound the compound being a nitrated acyclic, alicyclic or heterocyclic amine
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
本发明公开了一种二(1,5‑硝胺基四唑)‑四水合铜化钾化合物，其结构式如(I)所示：
Description
技术领域
本发明涉及一种含能材料，具体涉及一种二(1,5-硝胺基四唑)-四水合铜化钾化合物。
背景技术
起爆药是最敏感的化学能源，具有高敏感、高瞬发、高功率的特点，当受到外界较小的初始冲能如撞击、摩擦、针刺、火焰等激发时，会产生爆轰而引发次级装药爆炸。目前，在军用和民用领域广泛使用的起爆药为叠氮化铅和斯蒂芬酸铅，由于这两种起爆药含有有毒重金属元素——铅，导致使用该类起爆药对人员和环境造成严重污染，随着人们对武器弹药安全性和环境质量要求的提高，叠氮化铅和斯蒂芬酸铅的性能缺陷导致火工品及药剂勤务处理和使用中发生重大事故，也阻碍了火工品的发展，因此，各国科研工作者都在积极开展新型起爆药研究工作，期望设计出制备安全、感度适宜与高能输出、环保型的新一代起爆药品种。高氮四唑类衍生物结构含有大量的N-N和C-N键，具有芳香结构的稳定性，具有较好的热稳定性，较高的正生成热以及较大的产气量等特点，且其分解产物主要为清洁无污染的氮气，在构筑新型环保型起爆药方面具有广阔前景。5-硝基四唑具有化学潜能高、能量密度大等特点，高氮、低碳氢含量容易达到氧平衡，是一种具有潜力的含能材料配体，其中四(5-硝基四唑)·二水合铁(Ⅱ)化钠是一种基于5-硝基四唑设计制备的新型绿色、环保型起爆药。
朱雅红等《环保起爆药四(5-硝基四唑)·二水合铁(Ⅱ)化钠的合成和特性》，含能材料,2012,20(6),726-730公开了四(5-硝基四唑)·二水合铁(Ⅱ)化钠化合物的分子结构和爆轰性能，该化合物结构如下所示：
该化合物爆速为5550m/s，爆容为506L/kg。但是该化合物爆容较小、爆速较低。
发明内容
本发明所要解决的技术问题是克服背景技术的不足和缺陷，提供一种爆容较大、爆速较高的二(1,5-硝胺基四唑)-四水合铜化钾化合物。
本发明的二(1,5-硝胺基四唑)-四水合铜化钾化合物的合成路线如下：
以1,5-二硝胺基四唑为原料，首先与氢氧化钾反应生成1,5-二硝胺基四唑钾盐，然后与硫酸铜发生复分解反应生成二(1,5-硝胺基四唑)-四水合铜化钾。
本发明的二(1,5-硝胺基四唑)-四水合铜化钾化合物，其结构式如(I)所示：
本发明的二(1,5-硝胺基四唑)-四水合铜化钾的合成方法，包括以下步骤：
(1)1,5-二硝胺基四唑钾盐的合成
室温下，依次将1,5-二硝胺基四唑、甲醇加入反应瓶中，冰水浴冷却至0～5℃，滴加氢氧化钾的甲醇溶液，在0～5℃继续反应0.5h，过滤、甲醇洗、真空干燥得白色固体；其中1,5-二硝胺基四唑与氢氧化钾的摩尔比为1:2～3。
(2)二(1,5-硝胺基四唑)-四水合铜化钾的合成
室温下，将1,5-二硝胺基四唑钾盐、水加入反应瓶中，搅拌溶解后，加入硫酸铜，加热至50℃反应1h，冷却、过滤，减压浓缩滤液、冷却、过滤、干燥得绿色晶体；其中1,5-二硝胺基四唑钾盐与硫酸铜的摩尔比为1:1～2。
本发明的优点：
本发明的二(1,5-硝胺基四唑)-四水合铜化钾化合物爆容较大，其爆容为570L/kg，对比文件的四(5-硝基四唑)-二水合铁化钠的爆容为506L/kg；本发明的二(1,5-硝胺基四唑)-四水合铜化钾化合物能量较高，其爆速为7658m/s，对比文件的四(5-硝基四唑)·二水合铁(Ⅱ)化钠的爆速为5550m/s。
具体实施方式
以下结合实施例对本发明作进一步详细说明。
实施例1
(1)1,5-二硝胺基四唑钾盐的合成
室温下，依次将0.17g(0.89mmol)1,5-二硝胺基四唑、3.0mL甲醇加入反应瓶中，冰水浴冷却至0～5℃，滴加3.0mL含0.112g(2mmol)氢氧化钾的甲醇溶液，在0～5℃继续反应0.5h，过滤、甲醇洗、真空干燥得0.19g白色固体，收率为79.8％。
结构鉴定：
红外光谱：IR(KBr,cm-1),υ：1510,1439,1412,1367,1291,1236,1228,1099,1034,912,856
核磁光谱：13C NMR(DMSO-d6,125MHz),δ：154.42
元素分析：分子式CK2N8O4
理论值：C 4.51,N 42.08
实测值：C 4.62,N 42.03。
上述结构鉴定数据证实得到物质确实是1,5-二硝胺基四唑钾盐。
(2)二(1,5-硝胺基四唑)-四水合铜化钾的合成
室温下，将0.133g(0.5mmol)1,5-二硝胺基四唑钾盐、3.0mL水加入反应瓶中，搅拌溶解后，加入0.12g(0.75mmol)硫酸铜，加热至50℃反应1h，冷却、过滤，减压浓缩滤液、冷却、过滤、干燥得0.062g绿色晶体，收率为44.8％。
结构鉴定：
红外光谱：IR(KBr,cm-1),υ：3551,3430,1522,1440,1419,1352,1292,1109,1031,918,863
元素分析：分子式C2H8N16O12CuK2
理论值：C 4.07,H 1.37,N 37.99
实测值：C 4.18,H 0.31,N 37.83
单晶结构参数：该化合物晶体为单斜晶系，空间群为P2(1)/c，晶体学参数为： α＝90°，β＝104.458(2)°，γ＝90°，Z＝1，μ＝1.746mm-1，F(000)＝590。
上述结构鉴定数据证实得到物质确实是二(1,5-硝胺基四唑)-四水合铜化钾。
本发明二(1,5-硝胺基四唑)-四水合铜化钾的性能
(1)物化性能
外观：绿色晶体
溶解度：易溶于二甲基亚砜、水等；不溶于石油醚、正己烷、乙醚、乙酸乙酯、乙腈等
密度：2.135g/cm3 X-射线单晶衍射仪
(2)爆轰性能
爆速：密度为2.135g/cm3，计算爆速为7658m/s K-J方程
爆热：密度为2.135g/cm3，计算爆压为28.8GPa K-J方程
爆容：密度为2.135g/cm3，计算爆容为570L/kg K-J方程
本发明的二(1,5-硝胺基四唑)-四水合铜化钾的用途
本发明的二(1,5-硝胺基四唑)-四水合铜化钾具有爆容较大、能量较高等特点，有望作为新型环保起爆药。
Claims (1)
1.一种二(1,5-硝胺基四唑)-四水合铜化钾化合物，其结构式如(I)所示：
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| CN101434617A (zh) * | 2008-08-20 | 2009-05-20 | 西北大学 | 基于偶氮四唑的含能配合物及其应用 |
Non-Patent Citations (3)
| Title |
|---|
| Metal perchlorate complexes with 1,5-diaminotetrazole;Lavrenova, L. G.，等;《Zhurnal Neorganicheskoi Khimii》;19881231;第33卷(第10期);第2583-2586页 * |
| 含能配合物研究新进展;张同来，等;《含能材料》;20130430;第21卷(第2期);摘要，第138页表I * |
| 绿色四唑类起爆药研究的最新进展;张光全;《含能材料》;20110831;第19卷(第4期);第474页Scheme 5 * |
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