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CL-20 analogues: Structure - Thermal stability/decomposition mechanism relationships CL-20 类似物:结构-热稳定性/分解机理关系
Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-03-01 DOI: 10.1016/j.enmf.2024.02.008
Valery P. Sinditskii , Nikolai V. Yudin , Valery V. Serushkin , Anna O. Gubina , Anastasia D. Smirnova , Vladimir V. Parakhin , Gennadii A. Smirnov , Kyrill Yu Suponitsky , Aleksei B. Sheremetev

The thermal decomposition of a number of analogues of hexanitrohexaazaisowurtzitan (CL-20), in where one or more N-nitro groups have been replaced by another explosophoric unit (diverse N-alkylnitramine groups or N- trinitroethyl), has been studied by methods of isothermal and non-isothermal kinetics. It was found that replacing the N-nitro group with even a more thermally stable substituent leads to a decrease in the stability of the nitrated hexaazaisowurtzitane framework. It was suggested that the substituent distorts the symmetry of the strained hexaazaisowurtzitane cage, which affects the strength of the N–NO2 bond. When a substituent less stable than the N-nitro group in the parent CL-20 is installed, the initial stage of degradation is determined by the decomposition kinetics of this substituent. One of the objects of this study, 4,10-dinitro-2,6,8,12-tetrakis (2,2,2-trinitroethyl) −2,4,6,8,10,12-hexaazaisowurtzitane (8), was synthesized for the first time; it was fully characterized and also confirmed by X-ray structural data.

通过等温和非等温动力学方法,研究了一些六硝基六氮唑麝香草烷(CL-20)类似物的热分解,其中一个或多个-硝基被另一个爆炸单位(多种多样的-烷基硝胺基团或-三硝基乙基)取代。研究发现,即使用热稳定性更高的取代基取代-硝基,也会导致硝化六氮唑乌齐坦框架的稳定性降低。研究表明,取代基改变了六氮aisowurtzitane 应变笼的对称性,从而影响了 N-NO 键的强度。如果在母体 CL-20 中加入稳定性低于 N-硝基的取代基,降解的初始阶段将由该取代基的分解动力学决定。本研究首次合成了 4,10-二硝基-2,6,8,12-四(2,2,2-三硝基乙基)-2,4,6,8,10,12-六氮唑乌齐坦(),并对其进行了全面表征和 X 射线结构数据确认。
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引用次数: 0
3,7-Dinitroimidazo[1,2-b]pyridazine-6,8-diamine: A promising building block for advanced heat-resistant and low-sensitivity energetic materials 3,7-二硝基咪唑并[1,2-b]哒嗪-6,8-二胺:先进耐热和低敏感高能材料的理想构件
Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-03-01 DOI: 10.1016/j.enmf.2024.02.003
Jing Feng , Jie Sun , Lei Yang , Zhen-qi Zhang , Yang Liu , Qing Ma , Li-shuang Hu

Constructing heat-resistant fused heterocyclic compounds is increasingly fascinating in the field of energetic materials due to their excellent energy, high thermal stability, and low sensitivity, as well as high density in general. This study synthesized a novel heat-resistant explosive based on the imidazo [1,2-b]pyridazine fused ring,3,7-dinitroimidazo [1,2-b]pyridazine-6,8-diamine (5),using a three-step facile method. This compound exhibited a high density (1.856 g cm−3) and low mechanical sensitivities (IS = 40 J, FS = 350 N). Meanwhile, it displayed a higher thermal decomposition temperature of 324 °C compared to conventional heat-resistant explosive HNS (Td = 318 °C). In addition, it demonstrated significantly higher detonation performance (D = 8336 m s−1, p = 27.25 GPa) than both TNT (D = 6881 m s−1, p = 19.5 GPa) and HNS (D = 7612 m s−1, p = 24.3 GPa). Theoretical analysis shows that the intramolecular hydrogen bonding interactions of NH2–NO2–NH2 might be the main reason for the heat resistance of energetic materials based on the imidazo [1,2-b]pyridazine fused ring. The results of this study suggest that compound 5 is a promising building block and a candidate for heat-resistant energetic materials.

由于具有卓越的能量、高热稳定性、低敏感性和高密度等特点,构建耐热的融合杂环化合物在高能材料领域越来越具有吸引力。本研究采用三步法合成了一种基于咪唑并[1,2-]哒嗪融合环的新型耐热炸药,即 3,7-二硝基咪唑并[1,2-]哒嗪-6,8-二胺()。该化合物密度高(1.856 g cm),机械敏感性低(= 40 J,= 350 N)。同时,与传统的耐热炸药 HNS(= 318 ℃)相比,它的热分解温度更高(324 ℃)。此外,它的引爆性能(= 8336 秒,= 27.25 GPa)明显高于 TNT(= 6881 秒,= 19.5 GPa)和 HNS(= 7612 秒,= 24.3 GPa)。理论分析表明,NH-NO-NH 的分子内氢键相互作用可能是基于咪唑[1,2-]哒嗪融合环的高能材料具有耐热性的主要原因。研究结果表明,该化合物是一种很有前景的构筑基块,是耐热高能材料的候选材料。
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引用次数: 0
N-Acetonitrile functionalized 3-nitrotriazole: Precursor to nitrogen rich stable and insensitive energetic materials N-乙腈官能化 3-硝基三唑:富氮稳定不敏感高能材料的前体
Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-03-01 DOI: 10.1016/j.enmf.2024.01.003
Prachi Bhatia, Peddapothula Sahithi Priya, Priyanka Das, Dheeraj Kumar

In the field of energetic materials, prime attention has been given to the synthesis of environmentally compatible energetic materials having an adequate balance between energy and stability. For this purpose, nitrogen-rich heterocyclic rings have contributed as pivotal frameworks. Nitro-functionalized 1,2,4-triazoles have been profusely used as a constituent for synthesizing high-performing energetic materials (EMs) due to their high nitrogen content, good thermal stability, and modifiable sites via functionalization. Combination with a different energetic scaffold may provide an opportunity for accessible tailoring. In this work, in an effort to investigate the potential of 3-nitrotriazoles, its N-acetonitrile derivative 2 was synthesized, which was further converted to various explosophores. N-methylene-C bridged asymmetrically connected tetrazole (3) and 1,2,4-oxadiazole (9 and 10) based EMs have been synthesized. Further tuning of energetic properties via salt formation strategy was employed for the synthesis of compounds 47, 11 and 12. 1,2,4-oxadiazole-based compound 9 was also confirmed via X-ray diffraction analysis, and 10 was analyzed with 15N NMR spectroscopy. Compounds 3, 4, 5, 7 and 9 exhibited high thermal stabilities and were found to be insensitive towards impact and friction. Compounds 5, 6, and 10 exhibited detonation performance comparable to the conventional insensitive explosive TATB.

在高能材料领域,人们最关注的是合成与环境相容的高能材料,并在能量和稳定性之间取得适当的平衡。为此,富氮杂环作为关键框架做出了贡献。硝基官能化的 1,2,4- 三唑因其氮含量高、热稳定性好以及可通过官能化修饰位点而被广泛用作合成高性能高能材料(EMs)的成分。与不同的高能支架结合可为无障碍定制提供机会。在这项工作中,为了研究 3-硝基三唑的潜力,我们合成了其 N-乙腈衍生物 2,并进一步将其转化为各种爆炸物。基于 N-亚甲基-C 桥接的不对称连接四氮唑(3)和 1,2,4-恶二唑(9 和 10)的 EM 已被合成。在合成化合物 4-7、11 和 12 时,通过盐形成策略进一步调整了能量特性。基于 1,2,4-噁二唑的化合物 9 还通过 X 射线衍射分析得到了证实,而 10 则通过 15N NMR 光谱进行了分析。化合物 3、4、5、7 和 9 具有很高的热稳定性,并且对冲击和摩擦不敏感。化合物 5、6 和 10 的引爆性能与传统的不敏感炸药 TATB 相当。
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引用次数: 0
A density functional theory investigation of the substituent effect on acyclovir and guanine derivatives for applications on energetic materials 对阿昔洛韦和鸟嘌呤衍生物取代基效应的密度泛函理论研究,以应用于高能材料
Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-02-23 DOI: 10.1016/j.enmf.2024.01.002
Luciana Amorim da Silva, Gabriel Monteiro-de-Castro, Erick Galante, Itamar Borges Jr, Aline Cardoso Anastácio
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引用次数: 0
Cover Story 封面故事
Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-01-30 DOI: 10.1016/s2666-6472(23)00074-x
Abstract not available
无摘要
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引用次数: 0
Graphical Abstract 图表摘要
Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-01-30 DOI: 10.1016/s2666-6472(23)00075-1
Abstract not available
无摘要
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引用次数: 0
Synthesis, characterization, and thermal decomposition performance of 1,2,3-triazolyl-substituted 1,3,5-triazines with carbonyl, ester, and azide functional groups 具有羰基、酯和叠氮官能团的 1,2,3-三唑基取代 1,3,5- 三嗪的合成、表征和热分解性能
Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2023-12-15 DOI: 10.1016/j.enmf.2023.12.001
Tat'yana V. Sokolnikova, Maxim V. Penzik, Alexey G. Proidakov, Valery N. Kizhnyaev

Based on the organocatalytic reaction of enamine azide addition of 2,4,6-triazido-1,3,5-triazine to acetylacetone acetoacetic ester, we synthesized a series of previously unknown mono-, di-, and tri(1,2,3-triazolyl)-substituted-1,3,5-triazines that additionally carried carbonyl, ester, and azide groups. The structure of the obtained compounds was proved by NMR (1H, 13C) and IR spectroscopy, and the composition was confirmed by elemental analysis. With the aid of differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) coupled to mass spectrometry (TG-MS), we obtained data on the thermal behavior and decomposition mechanism for these compounds. We demonstrated that di(1,2,3-triazolyl)-substituted 1,3,5-triazines have an increased thermal stability and have higher values of decomposition onset temperature (220–250 °C) in comparison with tri(1,2,3-triazolyl)-substituted 1,3,5-triazines (180 °C and 160 °C, respectively).

基于 2,4,6-三氮杂-1,3,5-三嗪与乙酰丙酮乙酰乙酸酯的烯胺叠氮加成有机催化反应,我们合成了一系列之前未知的单-、二-和三(1,2,3-三唑基)-取代的-1,3,5-三嗪,这些化合物额外带有羰基、酯基和叠氮基团。核磁共振(1H、13C)和红外光谱证明了所获化合物的结构,元素分析确认了其成分。借助差示扫描量热法(DSC)和热重分析法(TGA)耦合质谱法(TG-MS),我们获得了这些化合物的热行为和分解机理数据。我们发现,与三(1,2,3-三唑基)取代的 1,3,5 三嗪(分别为 180 ℃ 和 160 ℃)相比,二(1,2,3-三唑基)取代的 1,3,5 三嗪具有更高的热稳定性和更高的分解起始温度(220-250 ℃)。
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引用次数: 0
Synthesis and characterization of 2-amino-4,5-bis(tetrazol-5-yl)-1,2,3-triazole: A high-nitrogen energetic material with low sensitivities and high thermal stability 2-amino-4,5-bis(tetrazol-5-yl)-1,2,3-triazole 的合成与表征:一种具有低敏感性和高热稳定性的高氮能材料
Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2023-12-15 DOI: 10.1016/j.enmf.2023.12.002
Xun Huang, Long Chen, Hai-feng Huang, Jun Yang

In this study, a high-nitrogen insensitive energetic material, 2-amino-4,5-bis(tetrazole-5-yl)-1,2,3-triazole (H2ABTT), was successfully synthesized by introducing the N-amino group on the 1,2,3-triazole ring. This compound exhibits excellent properties in many aspects. Compared to 4,5-bis(tetrazol-5-yl)-1,2,3-triazole (H3BTT), which has a decomposition temperature (Td) of 277 oC, nitrogen content of 75.11 %, density of 1.69 g cm−3, a detonation velocity of 8630 m s−1, a detonation pressure of 26.3 GPa, an impact sensitivity (IS) of 2 J, and a friction sensitivity (FS) of 240 N, H2ABTT exhibits higher thermal stability of Td:303 oC, higher nitrogen content of N%:76.35 %, higher density of 1.86 g cm−3, more desirable detonation properties (detonation pressure Dv: 9185 m s−1; detonation pressure p: 31.7 GPa), and lower mechanical sensitivities (IS > 100 J; FS > 360 N). Furthermore, H2ABTT outperforms insensitive explosive TATB (Dv = 8179 m s−1; p = 30.5 GPa; IS = 50 J; FS > 360 N) in some properties, making it a potential high-performance insensitive explosive. Besides, energetic salts 4–6 were successfully synthesized based on H2ABTT. The calculated results show that some of these salts even possess higher detonation performance compared to H2ABTT.

本研究通过在 1,2,3- 三唑环上引入 N-氨基,成功合成了一种高氮不敏感高能材料--2-氨基-4,5-双(四唑-5-基)-1,2,3-三唑(H2ABTT)。该化合物在许多方面都表现出优异的性能。与 4,5-双(四唑-5-基)-1,2,3-三唑(H3BTT)相比,其分解温度(Td)为 277 oC,含氮量为 75.11 %,密度为 1.69 g cm-3,爆速为 8630 m s-1,爆压为 26.H2ABTT 具有更高的热稳定性(Td:303 oC)、更高的氮含量(N%:76.35 %)、更高的密度(1.86 g cm-3)、更理想的起爆特性(起爆压力 Dv:9185 m s-1;起爆压力 p:31.7 GPa)和更低的机械敏感性(IS > 100 J;FS > 360 N)。此外,H2ABTT 在某些特性上优于不敏感炸药 TATB(Dv = 8179 m s-1;p = 30.5 GPa;IS = 50 J;FS > 360 N),使其成为一种潜在的高性能不敏感炸药。此外,基于 H2ABTT 成功合成了高能盐 4-6。计算结果表明,与 H2ABTT 相比,其中一些盐甚至具有更高的引爆性能。
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引用次数: 0
Influence of nitroamino−nitroimino tautomerism: A useful theoretical supplement for nitroamino-based energetic materials 硝基氨基-硝基氨基互变异构体的影响:对硝基氨基含能材料的有益理论补充
Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2023-11-01 DOI: 10.1016/j.enmf.2023.11.002
Ya-xi Wang, Xun Zhang, Jun-liang Liu, Meng-xin Xue, Lu Hu, Si-ping Pang
Nitroamino is an ideal high-energy group for constructing energetic compounds. The skeletal isomerization of nitroamino to nitroimino forms intramolecular HBs, thus resulting in better density, thermal stability and sensitivity. However, it is difficult to find nitroamino and nitroimino in the same environment for comparative analysis. A new compound, 5-Nitroamino-8-nitroimino-1,4-dihydropyrazino [2,3-d]pyridazine-2,3-dione (3), was designed and synthesized. The symmetric skeleton of pyrazino [2,3-d]pyridazine provides the same environment for both nitroamino and nitroimino groups. By using a variety of computational and graphical methods, a theoretical support for nitroamino-based energetic materials was produced by thoroughly examining the influence between nitroamino and nitroimino.
硝基氨基是构建含能化合物的理想高能基团。硝基氨基到硝基氨基的骨架异构化形成分子内HBs,从而产生更好的密度、热稳定性和灵敏度。然而,很难在同一环境中找到硝基氨基和硝基亚胺进行比较分析。设计合成了新的化合物5-硝基氨基-8-硝基氨基-1,4-二氢吡嗪[2,3-d]吡嗪-2,3-二酮(3)。pyrazino [2,3-d]吡嗪的对称骨架为硝基氨基和硝基氨基提供了相同的环境。通过多种计算和图解方法,深入研究了硝基氨基和硝基氨基之间的影响,为硝基氨基基含能材料的研究提供了理论支持。
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引用次数: 0
Preparation of NCh-B and NCh-B-Ti nanocomposites and their ignition and combustion performances NCh-B和NCh-B- ti纳米复合材料的制备及其点火燃烧性能
Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2023-11-01 DOI: 10.1016/j.enmf.2023.11.001
Yu-shu Xiong, Yong-qi Wang, Chong Wan, Wen-zhen Zhang, Zhao Qin, Su-hang Chen, Kang-zhen Xu
To overcome the agglomeration and insufficient combustion of nano-boron (n-B) powders, this study successfully prepared two novel types of boron-based nanocomposites using the acoustic resonance technology, namely high-substitute nitrochitosan/nano-boron (NCh-B) with ratios of 1:3, 1:5, 1:7, and 1:9 and nitrochitosan/nano-boron powder/nano-titanium (NCh-B-Ti) with Ti contents of 5 wt%, 10 wt%, 15 wt%, and 20 wt%. The structural morphologies, laser ignition, and combustion properties of the composites were systematically investigated. The results suggest that the addition of NCh can significantly improve the dispersion of n-B. NCh-B exhibited a higher combustion performance than n-B, as evidenced by their ignition delay and flame areas. When the laser power density was 81 W, NCh-B5-Ti15% exhibited a combustion time and an ignition delay of 240 ms and 5.5 ms respectively, which were higher and lower than those of NCh-B5 (199 ms and 17 ms, respectively). Furthermore, NCh-B5-Ti15% displayed a lower ignition delay than both n-B powders (12 ms) and NCh-B (11 ms), as well as brighter flames and a larger combustion area. Therefore, the addition of n-Ti can promote the combustion of the n-B powders, with the combustion products of NCh-B-Ti including H3BO3, B2O3, TiB2, and TiO. This study provides a new method for improving the ignition performance and combustion efficiency of n-B powders.
为了克服纳米硼(n-B)粉团聚和燃烧不充分的问题,本研究利用声共振技术成功制备了两种新型的硼基纳米复合材料,即高替代亚硝基壳聚糖/纳米硼(NCh-B)(比例分别为1:3、1:5、1:7和1:9)和亚硝基壳聚糖/纳米硼粉/纳米钛(NCh-B-Ti)(钛含量分别为5wt %、10wt %、15wt %和20wt %)。系统地研究了复合材料的结构形态、激光点火性能和燃烧性能。结果表明,NCh的加入能显著改善n-B的色散。NCh-B的燃烧性能优于n-B,其燃烧延迟和火焰面积均优于n-B。当激光功率密度为81 W时,NCh-B5- ti15%的燃烧时间和点火延迟分别为240 ms和5.5 ms,高于NCh-B5 (199 ms和17 ms)。NCh-B5-Ti15%比n-B粉末(12 ms)和NCh-B粉末(11 ms)具有更低的点火延迟,火焰更亮,燃烧面积更大。因此,n-Ti的加入可以促进n-B粉末的燃烧,NCh-B-Ti的燃烧产物包括H3BO3、B2O3、TiB2和TiO。该研究为提高n-B粉末的点火性能和燃烧效率提供了一种新的方法。
{"title":"Preparation of NCh-B and NCh-B-Ti nanocomposites and their ignition and combustion performances","authors":"Yu-shu Xiong, Yong-qi Wang, Chong Wan, Wen-zhen Zhang, Zhao Qin, Su-hang Chen, Kang-zhen Xu","doi":"10.1016/j.enmf.2023.11.001","DOIUrl":"https://doi.org/10.1016/j.enmf.2023.11.001","url":null,"abstract":"To overcome the agglomeration and insufficient combustion of nano-boron (n-B) powders, this study successfully prepared two novel types of boron-based nanocomposites using the acoustic resonance technology, namely high-substitute nitrochitosan/nano-boron (NCh-B) with ratios of 1:3, 1:5, 1:7, and 1:9 and nitrochitosan/nano-boron powder/nano-titanium (NCh-B-Ti) with Ti contents of 5 wt%, 10 wt%, 15 wt%, and 20 wt%. The structural morphologies, laser ignition, and combustion properties of the composites were systematically investigated. The results suggest that the addition of NCh can significantly improve the dispersion of n-B. NCh-B exhibited a higher combustion performance than n-B, as evidenced by their ignition delay and flame areas. When the laser power density was 81 W, NCh-B5-Ti15% exhibited a combustion time and an ignition delay of 240 ms and 5.5 ms respectively, which were higher and lower than those of NCh-B5 (199 ms and 17 ms, respectively). Furthermore, NCh-B5-Ti15% displayed a lower ignition delay than both n-B powders (12 ms) and NCh-B (11 ms), as well as brighter flames and a larger combustion area. Therefore, the addition of n-Ti can promote the combustion of the n-B powders, with the combustion products of NCh-B-Ti including H3BO3, B2O3, TiB2, and TiO. This study provides a new method for improving the ignition performance and combustion efficiency of n-B powders.","PeriodicalId":34595,"journal":{"name":"Energetic Materials Frontiers","volume":"9 8","pages":"0"},"PeriodicalIF":0.0,"publicationDate":"2023-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"135516019","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
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Energetic Materials Frontiers
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