CN115340501B - Energetic ionic salts based on bitriazole compounds and their synthesis methods - Google Patents
Energetic ionic salts based on bitriazole compounds and their synthesis methods Download PDFInfo
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 23
- 238000001308 synthesis method Methods 0.000 title claims abstract description 6
- 150000003839 salts Chemical class 0.000 title claims description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
- -1 ion salt Chemical class 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 13
- HAZRIBSLCUYMQP-UHFFFAOYSA-N 1,2-diaminoguanidine;hydron;chloride Chemical compound Cl.NN\C(N)=N/N HAZRIBSLCUYMQP-UHFFFAOYSA-N 0.000 claims abstract description 10
- UYPSFAUSXFPNSW-UHFFFAOYSA-N [N+](=O)([O-])C=1C(=NNN=1)C=1N(C(=NN=1)N)N Chemical compound [N+](=O)([O-])C=1C(=NNN=1)C=1N(C(=NN=1)N)N UYPSFAUSXFPNSW-UHFFFAOYSA-N 0.000 claims abstract description 10
- KUSAQLMAEMVDRO-UHFFFAOYSA-N 5-nitro-2h-triazole-4-carboxylic acid Chemical compound OC(=O)C1=NNN=C1[N+]([O-])=O KUSAQLMAEMVDRO-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000007864 aqueous solution Substances 0.000 claims abstract description 8
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims abstract description 7
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims abstract description 6
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000006396 nitration reaction Methods 0.000 claims abstract description 3
- 238000007363 ring formation reaction Methods 0.000 claims abstract 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- 239000003153 chemical reaction reagent Substances 0.000 claims description 10
- 229920000137 polyphosphoric acid Polymers 0.000 claims description 10
- 230000000802 nitrating effect Effects 0.000 claims description 9
- SFDJOSRHYKHMOK-UHFFFAOYSA-N nitramide Chemical compound N[N+]([O-])=O SFDJOSRHYKHMOK-UHFFFAOYSA-N 0.000 claims description 8
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 235000011007 phosphoric acid Nutrition 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims 2
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 claims 2
- SWGZHHCRMZDRSN-BTJKTKAUSA-N (Z)-but-2-enedioic acid 1-phenoxypropan-2-ylhydrazine Chemical compound OC(=O)\C=C/C(O)=O.NNC(C)COC1=CC=CC=C1 SWGZHHCRMZDRSN-BTJKTKAUSA-N 0.000 claims 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 11
- 230000015572 biosynthetic process Effects 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 9
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 7
- 238000005474 detonation Methods 0.000 abstract description 6
- PCVHZWLAPQWKMC-UHFFFAOYSA-N N([N+](=O)[O-])N1C(=NN=C1C1=NNN=C1[N+](=O)[O-])N Chemical compound N([N+](=O)[O-])N1C(=NN=C1C1=NNN=C1[N+](=O)[O-])N PCVHZWLAPQWKMC-UHFFFAOYSA-N 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract 2
- 229910021529 ammonia Inorganic materials 0.000 abstract 1
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 230000035945 sensitivity Effects 0.000 description 11
- 239000000243 solution Substances 0.000 description 8
- 238000000921 elemental analysis Methods 0.000 description 6
- QWENRTYMTSOGBR-UHFFFAOYSA-N 1H-1,2,3-Triazole Chemical compound C=1C=NNN=1 QWENRTYMTSOGBR-UHFFFAOYSA-N 0.000 description 5
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 125000000623 heterocyclic group Chemical group 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N DMSO Substances CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- 150000002391 heterocyclic compounds Chemical class 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 150000003852 triazoles Chemical class 0.000 description 2
- POCJOGNVFHPZNS-ZJUUUORDSA-N (6S,7R)-2-azaspiro[5.5]undecan-7-ol Chemical group O[C@@H]1CCCC[C@]11CNCCC1 POCJOGNVFHPZNS-ZJUUUORDSA-N 0.000 description 1
- 101100391174 Dictyostelium discoideum forC gene Proteins 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000003380 propellant Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- JDFUJAMTCCQARF-UHFFFAOYSA-N tatb Chemical compound NC1=C([N+]([O-])=O)C(N)=C([N+]([O-])=O)C(N)=C1[N+]([O-])=O JDFUJAMTCCQARF-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
- C07D249/10—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D249/14—Nitrogen atoms
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
本发明公开了一种基于联三唑类化合物的含能离子盐及其合成方法。其步骤为：（1）5‑硝基‑2H‑1,2,3‑三唑‑4‑羧酸与1,3‑二氨基胍盐酸盐经过环化反应制得5‑(5‑硝基‑2H‑1,2,3‑三唑‑4‑基)‑4H‑1,2,4‑三唑‑3,4‑二胺；（2）选择氮含量高的氨水、水合肼和羟胺水溶液，分别经过成盐反应制得相应含能离子盐。本发明合成的含能离子盐具有良好的爆轰性能及正生成焓；（3）5‑(5‑硝基‑2H‑1,2,3‑三唑‑4‑基)‑4H‑1,2,4‑三唑‑3,4‑二胺经硝化反应制得N‑(3‑氨基‑5‑(5‑硝基‑2H‑1,2,3‑三唑‑4‑基)‑4H‑1,2,4‑三唑‑4‑基)硝酰胺。本发明的合成过程简单，反应条件温和，安全性高，且原料经济易得，产物收率高，可以实现大规模生产，在含能材料领域有广泛应用。
The invention discloses an energetic ion salt based on bitriazole compounds and a synthesis method thereof. The steps are: (1) 5-(5-nitrogen) is prepared by cyclization reaction between 5-nitro-2H-1,2,3-triazole-4-carboxylic acid and 1,3-diaminoguanidine hydrochloride. base-2H-1,2,3-triazole-4-base)-4H-1,2,4-triazole-3,4-diamine; (2) Choose ammonia, hydrazine hydrate and hydroxylamine with high nitrogen content Aqueous solutions are subjected to salt-forming reactions to obtain corresponding energetic ion salts. The energetic ion salt synthesized by the invention has good detonation performance and positive enthalpy of formation; (3) 5-(5-nitro-2H-1,2,3-triazole-4-yl)-4H-1, 2,4-triazole-3,4-diamine is prepared through nitration reaction to produce N-(3-amino-5-(5-nitro-2H-1,2,3-triazole-4-yl)-4H -1,2,4-triazol-4-yl)nitramide. The synthesis process of the invention is simple, the reaction conditions are mild, the safety is high, the raw materials are economical and easy to obtain, the product yield is high, large-scale production can be achieved, and it is widely used in the field of energetic materials.
Description
技术领域Technical field
本发明属于含能材料领域，涉及一种基于联三唑类化合物的含能离子盐及其合成方法。The invention belongs to the field of energetic materials and relates to an energetic ion salt based on bitriazole compounds and a synthesis method thereof.
背景技术Background technique
新型含能材料在炸药、推进剂和烟火技术等领域具有很大的潜在价值，其设计和研究一直是全球许多研究小组关注的焦点。在过去的两个世纪中，高能材料的发展已经经历了三个阶段。TNT、TATB等第一代含能材料是基于苯骨架设计，具有低爆震性能。第二代含能材料衍生自环状和脂肪族硝胺结构，例如RDX和HMX，尽管增强了化合物的爆震性能，但稳定性却下降了。第三代化合物基于笼状硝胺结构具有高爆震性能和高灵敏度，例如CL-20。显然，每一代的到来都极大地促进了高能材料的快速发展。然而，在研究过程中，高能量与低灵敏度之间始终存在着严重的矛盾。为了开发新一代的高能化合物，应考虑许多特性，包括高能量，低灵敏度，良好的热稳定性，环境友好性和运输安全性。因此，必须考虑新的能量分子骨架的研究。研究发现富氮杂环骨架对新型高能密度材料起关键作用，因为它们在杂环骨架的N-N和N＝N键中存储有巨大能量，并具有正的形成热。New energetic materials have great potential value in the fields of explosives, propellants and pyrotechnics, and their design and research have been the focus of many research groups around the world. Over the past two centuries, the development of high-energy materials has gone through three stages. The first generation of energetic materials such as TNT and TATB are designed based on benzene skeleton and have low detonation performance. Second-generation energetic materials are derived from cyclic and aliphatic nitramine structures, such as RDX and HMX, and although they enhance the detonation properties of the compounds, their stability is reduced. Third-generation compounds based on caged nitramine structures have high detonation performance and high sensitivity, such as CL-20. Obviously, the arrival of each generation has greatly promoted the rapid development of high-energy materials. However, during the research process, there was always a serious contradiction between high energy and low sensitivity. In order to develop a new generation of high-energy compounds, many properties should be considered, including high energy, low sensitivity, good thermal stability, environmental friendliness, and transportation safety. Therefore, the study of new energetic molecular frameworks must be considered. The study found that nitrogen-rich heterocyclic skeletons play a key role in new high-energy-density materials because they store huge energy in the N-N and N=N bonds of the heterocyclic skeleton and have positive heat of formation.
富氮杂环化合物在新的高能化合物的发展中引起了极大的关注。其中三唑分子骨架表现出高氮含量，高密度和高生成焓，因此通常被选择为富氮杂环化合物结构的可能结构单元。三唑分子骨架包括1,2,3-三唑和1,2,4-三唑，1,2,3-三唑由于N-N-N(N3)结构比1,2,4-三唑(ΔfHm＝182kJ mol-1)具有更高的形成热。通过将1,2,3-三唑引入到含能分子中的这种方法可以改善含能化合物的爆轰性能，除了杂环骨架外对形成热的有效贡献，连接在主链上的氨基基团对化合物的性能也很重要。并且引入氨基可以促进分子内和分子间氢键的形成，从而可以提高化合物的密度和稳定性，进而改善化合物低灵敏度的问题。Nitrogen-rich heterocyclic compounds have attracted great attention in the development of new energetic compounds. Among them, the triazole molecular skeleton exhibits high nitrogen content, high density, and high enthalpy of formation, and is therefore often selected as a possible structural unit for the structure of nitrogen-rich heterocyclic compounds. The triazole molecular skeleton includes 1,2,3-triazole and 1,2,4-triazole. 1,2,3-triazole has a smaller NNN (N3) structure than 1,2,4-triazole (Δ f H m =182kJ mol -1 ) has a higher heat of formation. This method of introducing 1,2,3-triazole into energetic molecules can improve the detonation properties of energetic compounds, in addition to the effective contribution to the heat of formation of the heterocyclic skeleton, the amino group attached to the main chain Groups are also important to the properties of compounds. Moreover, the introduction of amino groups can promote the formation of intramolecular and intermolecular hydrogen bonds, thereby improving the density and stability of the compound, thus improving the problem of low sensitivity of the compound.
文献(From N-nitro to N-nitroamino:preparation of high-performanceenergetic materials by introducing nitrogen-containing ions[J].Angew.Chem.Int.Ed.2015,54,14513-14517)报导了一种化合物2,2’-二硝胺基-5,5’-二硝基-3,3’-联-1,2,4三唑，该化合物热分解温度为121℃，撞击感度3J，摩擦感度40N。该化合物较低的热稳定性和感度，导致储存和运输存在较大难度，实际生产过程中存在较大安全隐患，限制了实际应用。The literature (From N-nitro to N-nitroamino: preparation of high-performanceenergetic materials by introducing nitrogen-containing ions[J].Angew.Chem.Int.Ed.2015,54,14513-14517) reports a compound 2, 2'-dinitroamino-5,5'-dinitro-3,3'-bis-1,2,4 triazole, the thermal decomposition temperature of this compound is 121°C, the impact sensitivity is 3J, and the friction sensitivity is 40N. The compound's low thermal stability and sensitivity make it difficult to store and transport. It also poses potential safety hazards in the actual production process, limiting its practical application.
发明内容Contents of the invention
为改善联三唑化合物现有的稳定性问题，本发明目的在于提供一种基于联三唑类化合物的含能离子盐。In order to improve the existing stability problems of bitriazole compounds, the purpose of the present invention is to provide an energetic ion salt based on bitriazole compounds.
实现本发明目的的技术解决方案是：一种5-(5-硝基-2H-1,2,3-三唑-4-基)-4H-1,2,4-三唑-3,4-二胺含能离子盐(式1,2,3)，其结构如下：The technical solution to achieve the purpose of the present invention is: a kind of 5-(5-nitro-2H-1,2,3-triazole-4-yl)-4H-1,2,4-triazole-3,4 -Diamine energetic ion salt (formula 1, 2, 3), its structure is as follows:
一种N-(3-氨基-5-(5-硝基-2H-1,2,3-三唑-4-基)-4H-1,2,4-三唑-4-基)硝酰胺含能离子盐(式4,5)，其结构如下：A kind of N-(3-amino-5-(5-nitro-2H-1,2,3-triazol-4-yl)-4H-1,2,4-triazol-4-yl) nitramide Energetic ionic salt (formula 4, 5), its structure is as follows:
上述5-(5-硝基-2H-1,2,3-三唑-4-基)-4H-1,2,4-三唑-3,4-二胺含能离子盐(式1,2,3)的合成方法，包括：The above-mentioned 5-(5-nitro-2H-1,2,3-triazol-4-yl)-4H-1,2,4-triazole-3,4-diamine energetic ion salt (formula 1, The synthesis method of 2,3) includes:
(1)将5-硝基-2H-1,2,3-三唑-4-羧酸(a)与1,3-二氨基胍盐酸盐(b)在多聚磷酸反应体系下发生关环反应制备5-(5-硝基-2H-1,2,3-三唑-4-基)-4H-1,2,4-三唑-3,4-二胺(c)的步骤，(1) Combine 5-nitro-2H-1,2,3-triazole-4-carboxylic acid (a) and 1,3-diaminoguanidine hydrochloride (b) in a polyphosphoric acid reaction system The step of preparing 5-(5-nitro-2H-1,2,3-triazol-4-yl)-4H-1,2,4-triazole-3,4-diamine (c) by ring reaction,
(2)将5-(5-硝基-2H-1,2,3-三唑-4-基)-4H-1,2,4-三唑-3,4-二胺(c)与氨水、水合肼或羟胺水溶液分别发生成盐反应制备目标产物的步骤，(2) Mix 5-(5-nitro-2H-1,2,3-triazol-4-yl)-4H-1,2,4-triazole-3,4-diamine (c) with ammonia water , the step of preparing the target product through a salt-forming reaction of hydrazine hydrate or hydroxylamine aqueous solution respectively,
优选的，步骤(1)，多聚磷酸反应体系为比例为1.5g：0.5～5.5ml的五氧化二磷与正磷酸的混合体系。Preferably, in step (1), the polyphosphoric acid reaction system is a mixed system of phosphorus pentoxide and orthophosphoric acid in a ratio of 1.5g:0.5-5.5ml.
优选的，步骤(1)中，5-硝基-2H-1,2,3-三唑-4-羧酸与1,3-二氨基胍盐酸盐摩尔比为1：0.8～5.0。Preferably, in step (1), the molar ratio of 5-nitro-2H-1,2,3-triazole-4-carboxylic acid and 1,3-diaminoguanidine hydrochloride is 1:0.8-5.0.
优选的，步骤(1)中，反应温度为100～150℃。Preferably, in step (1), the reaction temperature is 100-150°C.
优选的，步骤(2)中，反应体系溶剂为无水甲醇、水、无水乙醇和乙腈中任意一种；反应温度是20℃～100℃。Preferably, in step (2), the reaction system solvent is any one of anhydrous methanol, water, anhydrous ethanol and acetonitrile; the reaction temperature is 20°C to 100°C.
上述N-(3-氨基-5-(5-硝基-2H-1,2,3-三唑-4-基)-4H-1,2,4-三唑-4-基)硝酰胺含能离子盐(式4,5)的合成方法，包括以下步骤：The above N-(3-amino-5-(5-nitro-2H-1,2,3-triazol-4-yl)-4H-1,2,4-triazol-4-yl) nitramide contains The synthesis method of energetic ionic salts (Formula 4, 5) includes the following steps:
(1)将5-硝基-2H-1,2,3-三唑-4-羧酸(a)与1,3-二氨基胍盐酸盐(b)在多聚磷酸反应体系下发生关环反应制备5-(5-硝基-2H-1,2,3-三唑-4-基)-4H-1,2,4-三唑-3,4-二胺(c)的步骤，(1) Combine 5-nitro-2H-1,2,3-triazole-4-carboxylic acid (a) and 1,3-diaminoguanidine hydrochloride (b) in a polyphosphoric acid reaction system The step of preparing 5-(5-nitro-2H-1,2,3-triazol-4-yl)-4H-1,2,4-triazole-3,4-diamine (c) by ring reaction,
(2)将5-(5-硝基-2H-1,2,3-三唑-4-基)-4H-1,2,4-三唑-3,4-二胺(c)与硝化试剂发生硝化反应制备N-(3-氨基-5-(5-硝基-2H-1,2,3-三唑-4-基)-4H-1,2,4-三唑-4-基)硝酰胺(d)的步骤，(2) Combine 5-(5-nitro-2H-1,2,3-triazol-4-yl)-4H-1,2,4-triazole-3,4-diamine (c) with nitrated The reagent undergoes nitration reaction to prepare N-(3-amino-5-(5-nitro-2H-1,2,3-triazol-4-yl)-4H-1,2,4-triazol-4-yl ) the step of nitramide (d),
(3)将N-(3-氨基-5-(5-硝基-2H-1,2,3-三唑-4-基)-4H-1,2,4-三唑-4-基)硝酰胺(d)与水合肼或羟胺水溶液分别发生成盐反应制备目标产物的步骤，(3) N-(3-amino-5-(5-nitro-2H-1,2,3-triazol-4-yl)-4H-1,2,4-triazol-4-yl) The step of preparing the target product through a salt-forming reaction between nitramide (d) and hydrazine hydrate or hydroxylamine aqueous solution respectively.
优选的，步骤(1)，多聚磷酸反应体系为比例为1.5g：0.5～5.5ml的五氧化二磷与正磷酸的混合体系。Preferably, in step (1), the polyphosphoric acid reaction system is a mixed system of phosphorus pentoxide and orthophosphoric acid in a ratio of 1.5g:0.5-5.5ml.
优选的，步骤(1)中，5-硝基-2H-1,2,3-三唑-4-羧酸与1,3-二氨基胍盐酸盐摩尔比为1：0.8～5.0。Preferably, in step (1), the molar ratio of 5-nitro-2H-1,2,3-triazole-4-carboxylic acid and 1,3-diaminoguanidine hydrochloride is 1:0.8-5.0.
优选的，步骤(1)中，反应温度为100～150℃。Preferably, in step (1), the reaction temperature is 100-150°C.
优选的，步骤(2)中，硝化试剂为100％HNO3、98％H2SO4/HNO3和98％HNO3中任意一种；5-(5-硝基-2H-1,2,3-三唑-4-基)-4H-1,2,4-三唑-3,4-二胺与硝化试剂的投料比为1g：5～25ml；反应温度-15℃～-5℃。Preferably, in step (2), the nitrating reagent is any one of 100% HNO 3 , 98% H 2 SO 4 /HNO 3 and 98% HNO 3 ; 5-(5-nitro-2H-1,2, The feeding ratio of 3-triazole-4-yl)-4H-1,2,4-triazole-3,4-diamine and nitrating reagent is 1g:5~25ml; the reaction temperature is -15℃~-5℃.
优选的，步骤(3)中，反应体系溶剂为无水甲醇、水、无水乙醇和乙腈中任意一种；反应温度是20℃～100℃。Preferably, in step (3), the reaction system solvent is any one of anhydrous methanol, water, anhydrous ethanol and acetonitrile; the reaction temperature is 20°C to 100°C.
与现有技术相比，本发明的创新点在于：Compared with the existing technology, the innovation points of the present invention are:
(1)本发明基于1,2,3-三唑和1,2,4-三唑分子骨架相结合合成了新的高能低感含能化合物。相比于已报道的联1,2,4-三唑化合物，热稳定性、撞击感度、摩擦感度均有所提高。(1) The present invention synthesizes new high-energy and low-sensitivity energetic compounds based on the combination of 1,2,3-triazole and 1,2,4-triazole molecular skeletons. Compared with reported 1,2,4-triazole compounds, the thermal stability, impact sensitivity, and friction sensitivity are all improved.
(2)本发明中含能离子盐的合成进一步提高了化合物的爆轰性能。(2) The synthesis of energetic ion salts in the present invention further improves the detonation performance of the compound.
(3)本发明中通过对比不同的硝化试剂以及投料量，确定了最佳硝化试剂，最大化的提高了目标化合物的产率。(3) In the present invention, by comparing different nitrating reagents and feeding amounts, the optimal nitrating reagent is determined, which maximizes the yield of the target compound.
附图说明Description of the drawings
图1为5-(5-硝基-2H-1,2,3-三唑-4-基)-4H-1,2,4-三唑-3,4-二胺肼盐的单晶图。Figure 1 is a single crystal diagram of 5-(5-nitro-2H-1,2,3-triazol-4-yl)-4H-1,2,4-triazole-3,4-diamine hydrazine salt .
具体实施方式Detailed ways
本发明所述的含能离子盐的合成路线如下所示：The synthesis route of the energetic ion salt according to the present invention is as follows:
实施例1Example 1
多聚磷酸反应体系：将五氧化二磷(5.0g，35.0mmol)在磷酸(15.0g，153.0mmol)中缓慢融化，并将溶液温度加热至50℃。Polyphosphoric acid reaction system: Slowly melt phosphorus pentoxide (5.0g, 35.0mmol) in phosphoric acid (15.0g, 153.0mmol), and heat the solution temperature to 50°C.
将5-硝基-2H-1,2,3-三唑-4-羧酸(1.57g，10.0mmol，1.0倍当量)和二氨基胍一盐酸盐(1.88g，15.0mmol，1.5倍当量)的混合物缓慢添加至多聚磷酸反应体系。然后将粘性混合液逐渐升高至120℃。将混合物在120℃下搅拌10h，然后冷却至室温。将反应液倒入冰水(20.0mL)中，然后用浓氢氧化钠溶液调节至pH＝2。过滤沉淀物，用大量水洗涤并真空干燥，得到5-(5-硝基-2H-1,2,3-三唑-4-基)-4H-1,2,4-三唑-3,4-二胺(c)为白色粉末，产率61.9％。5-Nitro-2H-1,2,3-triazole-4-carboxylic acid (1.57g, 10.0mmol, 1.0 times the equivalent) and diaminoguanidine monohydrochloride (1.88g, 15.0mmol, 1.5 times the equivalent ) mixture was slowly added to the polyphosphoric acid reaction system. The viscous mixture was then gradually raised to 120°C. The mixture was stirred at 120 °C for 10 h and then cooled to room temperature. The reaction solution was poured into ice water (20.0 mL), and then adjusted to pH=2 with concentrated sodium hydroxide solution. The precipitate was filtered, washed with a large amount of water and dried under vacuum to obtain 5-(5-nitro-2H-1,2,3-triazol-4-yl)-4H-1,2,4-triazole-3, 4-Diamine (c) is a white powder with a yield of 61.9%.
1H NMR(500MHz,DMSO-d6):δ＝8.19(s,2H),5.86(s,2H)ppm.13C NMR(125MHz,DMSO-d6):δ＝152.80,151.57,144.75,125.87ppm.IR(KBr):v＝3431,3318,3218,1683,1633,1504,1380,1251,1196,1132,996,908,809,776,680,649cm-1；elemental analysiscalcd(％)for C4H5N9O2(211):C 22.75,H 2.39,N 59.70；found:C 22.72,H 2.38,N59.70。 1 H NMR (500MHz, DMSO-d 6 ): δ = 8.19 (s, 2H), 5.86 (s, 2H) ppm. 13 C NMR (125MHz, DMSO-d 6 ): δ = 152.80, 151.57, 144.75, 125.87 ppm.IR (KBr): v=3431,3318,3218,1683,1633,1504,1380,1251,1196,1132,996,908,809,776,680,649cm -1 ; elemental analysiscalcd (%) for C 4 H 5 N 9 O 2 (211 ):C 22.75, H 2.39, N 59.70; found: C 22.72, H 2.38, N59.70.
实施例2Example 2
在25℃下向0.21g(1.0mmol)5-(5-硝基-2H-1,2,3-三唑-4-基)-4H-1,2,4-三唑-3,4-二胺(c)的悬浮水溶液中搅拌下缓慢分别滴加氨水、水合肼、羟胺水溶液。将反应溶液缓慢升至75℃并在75℃下保持2小时，然后冷却至室温，析出大量固体，过滤沉淀物，用少量水洗涤，并在空气中干燥48小时。依次获得相关含能离子盐(1-3)。其中，将5-(5-硝基-2H-1,2,3-三唑-4-基)-4H-1,2,4-三唑-3,4-二胺肼盐(2)进行重结晶，所得晶体结构见图1。Add 0.21g (1.0mmol) 5-(5-nitro-2H-1,2,3-triazol-4-yl)-4H-1,2,4-triazole-3,4- at 25°C. To the suspended aqueous solution of diamine (c), ammonia water, hydrazine hydrate, and hydroxylamine aqueous solution were slowly added dropwise while stirring. The reaction solution was slowly raised to 75°C and kept at 75°C for 2 hours, then cooled to room temperature, a large amount of solid precipitated, the precipitate was filtered, washed with a small amount of water, and dried in the air for 48 hours. Relevant energetic ion salts (1-3) are obtained in sequence. Among them, 5-(5-nitro-2H-1,2,3-triazol-4-yl)-4H-1,2,4-triazole-3,4-diamine hydrazine salt (2) is After recrystallization, the obtained crystal structure is shown in Figure 1.
5-(5-硝基-2H-1,2,3-三唑-4-基)-4H-1,2,4-三唑-3,4-二胺氨盐(1)：5-(5-nitro-2H-1,2,3-triazol-4-yl)-4H-1,2,4-triazole-3,4-diamine ammonium salt (1):
1H NMR(d6-DMSO,25℃):δ＝7.20(s),5.73(s,2H),5.30(s,2H)ppm.13C NMR(d6-DMSO,25℃):δ＝155.22,152.04,143.79,129.65ppm.IR(KBr):v＝3405,2395,2017,1740,1583,1313,1276,1162,1214,1121,1065,1028,973,849,776,739,712,641,502,458cm-1；elemental analysis calcd(％)for C4H8N10O2(228):C 21.06,H 3.53,N 63.39；found:C21.04,H 3.55,N63.39。 1 H NMR (d 6 -DMSO, 25°C): δ = 7.20 (s), 5.73 (s, 2H), 5.30 (s, 2H) ppm. 13 C NMR (d 6 -DMSO, 25°C): δ = 155.22,152.04,143.79,129.65ppm.IR(KBr):v＝3405,2395,2017,1740,1583,1313,1276,1162,1214,1121,1065,1028,973,849,776,739,712,641 ,502,458cm -1 ; elemental analysis calcd(% )for C 4 H 8 N 10 O 2 (228): C 21.06, H 3.53, N 63.39; found: C21.04, H 3.55, N63.39.
5-(5-硝基-2H-1,2,3-三唑-4-基)-4H-1,2,4-三唑-3,4-二胺肼盐(2)：5-(5-nitro-2H-1,2,3-triazol-4-yl)-4H-1,2,4-triazole-3,4-diamine hydrazine salt (2):
1H NMR(500MHz,DMSO-d6):δ＝7.10(s),5.73(s,2H),5.30(s,2H)ppm.13C NMR(125MHz,DMSO-d6):δ＝155.06,152.00,143.76,129.60ppm.IR(KBr):v＝3405,3266,3192,1654,1614,1553,1494,1448,1357,1257,1193,1126,1024,967,826,762,703cm-1；elemental analysis calcd(％)for C4H9N11O2(243):C 19.76,H 3.73,N 63.36；found:C19.75,H 3.72,N 63.36。 1 H NMR (500MHz, DMSO-d 6 ): δ = 7.10 (s), 5.73 (s, 2H), 5.30 (s, 2H) ppm. 13 C NMR (125MHz, DMSO-d 6 ): δ = 155.06, 152.00,143.76,129.60ppm.IR(KBr):v＝3405,3266,3192,1654,1614,1553,1494,1448,1357,1257,1193,1126,1024,967,826,762,703cm -1 ; elemental analysis calc d(% )for C 4 H 9 N 11 O 2 (243): C 19.76, H 3.73, N 63.36; found: C 19.75, H 3.72, N 63.36.
5-(5-硝基-2H-1,2,3-三唑-4-基)-4H-1,2,4-三唑-3,4-二胺羟胺盐(3)：5-(5-nitro-2H-1,2,3-triazol-4-yl)-4H-1,2,4-triazole-3,4-diamine hydroxylamine salt (3):
1H NMR(500MHz,DMSO-d6):δ＝9.11(s),6.20(s,2H),5.41(s,2H)ppm.13C NMR(125MHz,DMSO-d6):δ＝154.22,152.13,143.93,128.69ppm.IR(KBr):v＝3426,3321,3119,1671,1626,1502,1454,1362,1239,1186,1101,1030,987,814,791,697cm-1.elementalanalysis calcd(％)for C4H8N10O3(244):C 19.68,H 3.30,N 57.36；found:C 19.66,H3.73,N 57.35。 1 H NMR (500MHz, DMSO-d 6 ): δ = 9.11 (s), 6.20 (s, 2H), 5.41 (s, 2H) ppm. 13 C NMR (125MHz, DMSO-d 6 ): δ = 154.22, 152.13,143.93,128.69ppm.IR(KBr):v＝3426,3321,3119,1671,1626,1502,1454,1362,1239,1186,1101,1030,987,814,791,697cm -1 .elementalanalysis calcd(%)for C 4 H 8 N 10 O 3 (244): C 19.68, H 3.30, N 57.36; found: C 19.66, H3.73, N 57.35.
实施例3Example 3
向15mL的100wt％硝酸中缓慢加入1.57g的5-(5-硝基-2H-1,2,3-三唑-4-基)-4H-1,2,4-三唑-3,4-二胺(c),在-15℃下反应20小时。100mL的冰水对反应液淬灭，有大量固体析出，过滤即得N-(3-氨基-5-(5-硝基-2H-1,2,3-三唑-4-基)-4H-1,2,4-三唑-4-基)硝酰胺(d)，产量为1.98g(产率：89％)。Slowly add 1.57g of 5-(5-nitro-2H-1,2,3-triazol-4-yl)-4H-1,2,4-triazole-3,4 to 15mL of 100wt% nitric acid. -Diamine (c), react at -15°C for 20 hours. Quench the reaction solution with 100 mL of ice water, and a large amount of solid will precipitate. Filter to obtain N-(3-amino-5-(5-nitro-2H-1,2,3-triazol-4-yl)-4H. -1,2,4-triazol-4-yl)nitramide (d), yield 1.98 g (yield: 89%).
1H NMR(500MHz,DMSO-d6):δ＝8.39(s,2H)ppm.13C NMR(125MHz,DMSO-d6):δ＝151.68,149.46,140.31,126.35ppm.IR(KBr):v＝3433,3327,3239,1684,1544,1514,1436,1351,1289,1253,1148,1072,975,897,825,769,714cm-1；elemental analysis calcd(％)for C4H4N10O4(256):C 18.76,H 1.57,N 54.68；found:C 18.73,H 1.56,N 54.68。 1 H NMR (500MHz, DMSO-d 6 ): δ = 8.39 (s, 2H) ppm. 13 C NMR (125MHz, DMSO-d 6 ): δ = 151.68, 149.46, 140.31, 126.35ppm. IR (KBr): v＝3433,3327,3239,1684,1544,1514,1436,1351,1289,1253,1148,1072,975,897,825,769,714cm -1 ; elemental analysis calcd (%) for C 4 H 4 N 10 O 4 (256): C 18.76, H 1.57, N 54.68; found: C 18.73, H 1.56, N 54.68.
实施例4Example 4
本实施例与实施例3基本相同，唯一不同的是硝化试剂是98wt％H2SO4/HNO3，得到目标产物(d)，收率72％。This example is basically the same as Example 3. The only difference is that the nitrating reagent is 98wt% H 2 SO 4 /HNO 3 , and the target product (d) is obtained with a yield of 72%.
实施例5Example 5
本实施例与实施例3基本相同，唯一不同的是硝化试剂是98wt％HNO3，得到目标产物(d)，收率63％。This example is basically the same as Example 3. The only difference is that the nitrating reagent is 98wt% HNO 3 to obtain the target product (d) with a yield of 63%.
实施例6Example 6
在25℃下向0.26g(1.0mmol)化合物(d)的悬浮甲醇溶液中搅拌下缓慢分别滴加水合肼、羟胺水溶液。将反应溶液在室温下搅拌2小时，过滤沉淀物，用少量水洗涤，并在空气中干燥48小时。依次获得相关含能离子盐(4,5)To the suspended methanol solution of 0.26 g (1.0 mmol) of compound (d) at 25°C, hydrazine hydrate and hydroxylamine aqueous solution were slowly added dropwise while stirring. The reaction solution was stirred at room temperature for 2 hours, and the precipitate was filtered, washed with a small amount of water, and dried in the air for 48 hours. Obtain related energetic ion salts (4,5) in sequence
N-(3-氨基-5-(5-硝基-2H-1,2,3-三唑-4-基)-4H-1,2,4-三唑-4-基)硝酰胺二肼盐(4)N-(3-Amino-5-(5-nitro-2H-1,2,3-triazol-4-yl)-4H-1,2,4-triazol-4-yl)nitramide dihydrazine salt(4)
1H NMR(500MHz,DMSO-d6):δ＝6.75(s)ppm.13C NMR(125MHz,DMSO-d6):δ＝157.09,152.35,143.48,128.36ppm.IR(KBr):v＝3310,3232,2809,1573,1455,1420,1355,1207,1168,1133,1024,991,960,919,858,782,740cm-1；elemental analysis calcd(％)forC4H12N14O4(320):C 15.00,H 3.78,N 61.24；found:C 15.03,H 3.75,N 61.25。 1 H NMR (500MHz, DMSO-d 6 ): δ = 6.75 (s) ppm. 13 C NMR (125 MHz, DMSO-d 6 ): δ = 157.09, 152.35, 143.48, 128.36ppm. IR (KBr): v＝ 3310,3232,2809,1573,1455,1420,1355,1207,1168,1133,1024,991,960,919,858,782,740cm -1 ; elemental analysis calcd(%)forC 4 H 12 N 14 O 4 (320):C 15.00, H 3.78 ,N 61.24;found:C 15.03,H 3.75,N 61.25.
N-(3-氨基-5-(5-硝基-2H-1,2,3-三唑-4-基)-4H-1,2,4-三唑-4-基)硝酰胺二羟胺盐(5)N-(3-Amino-5-(5-nitro-2H-1,2,3-triazol-4-yl)-4H-1,2,4-triazol-4-yl)nitramidedihydroxylamine Salt(5)
1H NMR(500MHz,DMSO-d6):δ＝9.13(s)ppm.13C NMR(125MHz,DMSO-d6):δ＝152.66,149.90,143.87,126.42ppm.IR(KBr):v＝3520,3356,3024,2808,1447,1363,1312,1174,1129,1034,932,882,789,741cm-1；elemental analysis calcd(％)for C4H10N12O6(322):C14.91,H 3.13,N 52.17；found:C 14.93,H 3.14,N 52.18。 1 H NMR (500MHz, DMSO-d 6 ): δ = 9.13 (s) ppm. 13 C NMR (125 MHz, DMSO-d 6 ): δ = 152.66, 149.90, 143.87, 126.42ppm. IR (KBr): v＝ 3520,3356,3024,2808,1447,1363,1312,1174,1129,1034,932,882,789,741cm -1 ; elemental analysis calcd(%)for C 4 H 10 N 12 O 6 (322):C14.91,H 3.13 ,N 52.17; found:C 14.93,H 3.14,N 52.18.
下面的表1给出了各含能离子盐的性能。Table 1 below gives the properties of each energetic ion salt.
表1.化合物的性能Table 1. Properties of compounds
a热分解速率：5℃min-1；b生成焓；c撞击感度；d摩擦感度；e爆速；f爆压；g密度。 a Thermal decomposition rate: 5℃min -1 ; b Generation enthalpy; c Impact sensitivity; d Friction sensitivity; e Explosion velocity; f Explosion pressure; g Density.
综上，本发明提供了一种基于1,2,3-三唑和1,2,4-三唑相结合的化合物含能离子盐的合成方法，并对反应条件进行了优化，同时在在硝化过程中采用了不同的硝化试剂，优化了硝化条件，使目标产物的产率得到最大程度提高。In summary, the present invention provides a method for synthesizing energetic ionic salts of compounds based on the combination of 1,2,3-triazole and 1,2,4-triazole, and optimizes the reaction conditions. Different nitrating reagents were used during the nitrification process, and the nitrification conditions were optimized to maximize the yield of the target product.
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| CN103483264A (en) * | 2012-06-12 | 2014-01-01 | 北京理工大学 | Energetic ion salts of 1-nitramine-2, 4-dimetridazloe and preparation method thereof |
| CN106188009A (en) * | 2016-07-05 | 2016-12-07 | 北京理工大学 | 3,4 dinitro 1 (1H tetrazolium 5 base) 1H pyrazoles 5 amine are containing energy ion salt preparation method and performance |
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| 5，5′-二氨基-4，4′-二硝胺基-3，3′-联-1，2，4-三唑三氨基胍盐（TAGAT）的 晶体结构及爆轰性能;薛钰冰，等;《含能材料》;第28卷(第7期);638-643 * |
| Energetic Materials Based on 5,5’-Diamino-4,4’-dinitramino-3,3’-bi- 1,2,4-triazole;Thomas M. Klapotke，等;《Chem. Asian J.》;第11卷;844-851，figure2，scheme1，table1 * |
| Thermal stabilization of energetic materials by the aromatic nitrogen-rich 4,4’,5,5‘-tetraamino-3,3’-bi- 1,2,4-triazolium cation;Thomas M. Klapotke, 等;《J. Mater. Chem. A》;第3卷;2658–2668，scheme1，table2 * |
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