1,5-Diazido-3-oxopentane (AZDEGDN) is a promising energetic plasticizer widely used in explosive formulations due to its low sensitivity, low glass transition temperature, and high thermal stability. However, its application in solid propellants requires further investigation. In this study, the physicochemical properties of AZDEGDN based propellant samples were characterized using differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), vacuum stability test (VST), hot-stage polarized light microscopy (HSPLM), rheological testing, dynamic mechanical analysis (DMA), and accelerated aging test. The study shows that AZDEGDN exhibits chemical compatibility with glycidyl azide polymer (GAP), poly(3,3-bis(azidomethyl)oxetane)-co-tetrahydrofuran (PBT), polyethylene glycol (PEG), poly(tetrahydrofuran)-co-ethylene oxide (PET), aluminum (Al), ammonium perchlorate (AP), dihydroxylammonium 5,5′-bistetrazole-1,1′-diolate (TKX-50) and 1,3,5,7-tetranitro-1,3,5,7-tetrazocane (HMX). Notably, the AZDEGDN/GAP mixture demonstrates a 99.42 % reduction in viscosity compared to pure GAP, and the plasticizing efficiency of AZDEGDN is higher than butylnitroxyethyl nitramine (Bu-NENA). The propellant containing PET and AZDEGDN exhibits a glass transition temperature of -79 °C. VST results confirmed the good thermal stability of the solid propellant samples (gas evolution < 0.6 mL). HSPLM imaging revealed that AZDEGDN based propellant only shows mild degradation and expansion after heating from 30 °C to 300 °C. Accelerated aging test indicated robust physical compatibility between AZDEGDN and propellant components, with superior resistance to migration during long-term storage. In conclusion, AZDEGDN is a promising energetic plasticizer with good compatibility and plasticization efficiency which can be used in polyether-based solid propellants.

Geminal dinitropropyl ester plasticizers (DNPEPs) possess excellent energetic performances which provide good potentials as insensitive plasticizer. In this study, we design and synthesize DNPEPs with different alkane chain parts, and systematically investigate their structure-property relationships. Results show that DNPEPs have impact sensitivities all higher than 25.2 J, thermal decomposition tem-peratures all higher than 254 degrees C, and glass transition temperatures (Tg) lower than-90 degrees C. Furthermore, the effects of DNPEPs as plasticizer are studied on hydroxyl terminated polybutadiene (HTPB) in detail, including the viscosity, glass transition temperatures and others. It is noteworthy that 2,2-dinitropropyl nonanoate (DNPNc) among these DNPEPs exhibits the most expected simultaneous tuning effects on both viscosity and Tg of HTPB systems, providing favorable potentials to replace the con-ventional plastizers as dioctyl sebacate (DOS) in the HTPB based propellants and explosives.(c) 2022 The Chemical Industry and Engineering Society of China, and Chemical Industry Press Co., Ltd. All rights reserved.

For the development of safe, non-toxic and environmentally friendly gas generators, a nitrogen-rich compound 5,7-diamine-2-nitro-1,2,4-triazolo[1,5-a]-1,3,5-triazine (ANTT) was synthesized from 3,5-diamine-1,2,4-triazole in two steps. The structure of ANTT was comprehensively characterized and well investigated by X-ray diffraction. The thermal stability, detonation properties and mechanical sensitivities of ANTT were finely studied. ANTT, enjoyed with a high content of nitrogen (57.13%), as well as a high decomposition temperature of 358.5 °C, high self-accelerating decomposition temperature of 340.3 °C, high critical temperature of thermal explosion 342.2 °C, high apparent activation energy of 512.23 kJ•mol−1 and low sensitivity toward destructive mechanical stimuli (IS > 60 J; FS > 360 N), is promising candidate as gas generator.

以5-氨基四唑为原料,经氧化、还原及中和反应合成了5,5'-肼基双四唑二羟胺盐(HBT-HA),并利用红外光谱、核磁共振、元素分析对产物进行了表征.利用差示扫描量热法(DSC)、热失重法(TG)对HBT-HA进行了热分解研究,并结合Kissinger法和Ozawa法及相关方程计算了HBT-HA的热动力学参数、热爆炸临界温度;基于实测密度(ρ=1.519g/cm3)和预估生成焓(ΔHf=1877.3kJ/mol),利用Explo5(V6.04)软件预估了HBT-HA的爆速、爆压和爆热,采用BAM撞击感度测试仪测试了HBT-HA的感度;优化了HBT-HA的合成工艺,并测试了HBT-HA与双基推进剂的相容性.结果表明,中和反应较佳反应条件为:以水为反应溶剂,反应温度为10～15℃,n(HBT):n(NH2 OH)=1:5时反应1 h;HBT-HA的热分解峰温为241.7℃,活化能、指前因子、热爆炸临界温度分别为271.18 kJ/mol、63.90 s-1、513.15 K;预估的爆速、爆压和爆热分别为9118 m/s、33.1 GPa和10.65 MJ/kg,HBT-HA的撞击感度大于60.0 J;相容性测试结果表明,HBT-HA可提高双基推进剂的热稳定性.

With nitroethane as starting material, energetic plasticizer 2, 2-dinitropropyl trifluoropropanoate (DNPTFP) was designed and synthesized via condensation reaction, oxidation reaction and esterification reaction. Its structure was characterized and confirmed by means of nuclear magnetic resonance (NMR ) Fourier transform infrared spectroscopy ( FTIR ) and elemental analysis. Optimization on the synthesis process of DNPTFP was conducted, and the optimal reaction conditions for the esterification reaction were determined as follows: taking toluene as reaction solvent, n(2, 2-dinitropropan-l-ol) :n( trifluoropropanoic acid)=1: 1.10, the addition of concentrated H2SO4 catalyst was 5.0% (mass fraction) , the reaction temperature was 110 degrees C , the reaction time was 10 h, and the yield and purity of DNPTFP was 75.2% and 99.0%, respectively. Thermal analysis determined that the glass transition temperature (T-g) was -80.5 degrees C and thermal decomposition peak temperature was 267.59 degrees C. While mechanical sensitivities showed that the impact sensitivity was measured as H-50 =125.9 cm, the friction sensitivity was 0. Those results indicated that DNPTFP had good thermal properties as well as insensitive mechanical sensitivities. Besides, as miscibility test, viscosity and T. measurements turned out, DNPTFP had good miscibility with glycide azide polymer(GAP) , and demonstrated notable adjust ability on the viscosity and T-g of GAP. Moreover, along with higher mixing ratio of DNPTFP, lower fluidity activation energy and higher plasticizing efficiency was achieved. Therefore, DNPTFP exhibited excellent plasticizing effect on GAP, which indicating good potential application in GAP based explosives and propellant.

针对发射药、推进剂、炸药光固化3D打印技术,按照光固化3D打印技术的特点和应用方向,综述火炸药光固化3D打印技术的研究进展.概述立体光固化成型技术、数字光处理技术、连续液面制造技术的成型原理以及工艺特点,分析光固化3D打印火炸药研究存在的问题,提出光固化3D打印火炸药采用新型黏合剂的重要性,总结光固化黏合剂的发展方向和趋势,并对火炸药光固化3D打印技术发展方向进行预测.指出火炸药光固化3D打印技术应按照火炸药的应用背景,对光固化3D打印火炸药用含能黏合剂设计与制备、黏合剂与固体填料表界面作用、工艺适配性、性能精细化表征进行系统化研究,为光固化3D打印技术在火炸药中的应用提供参考.

Novel geminal dinitro ester energetic plasticizers (DNEPs) were designed with different alkane lengths in the mainchain, namely 2,2-dinitropropyl acetate (DNPAc), 2,2-dinitropropyl propionate (DNPPc), and 2,2-dinitropropyl propionate (DNPBc). Due to the incorporation of ester and dinitro groups, these three DNEPs were expected to possess high heat of formations and thermal decomposition temperatures (Tp) and lower glass transition temperatures (Tg). Likewise, their impact sensitivities were all measured as higher than 25.2 J. Due to the maximum alkane length of DNPBc, DNPBc possesses the highest Tp and the lowest Tg. As plasticizers for glycidyl azide polymer (GAP), DNEPs significantly improve the viscosity and Tg of GAP. Particularly, the plasticizing efficiency of DNPBc is higher than that of the reported N-butyl nitroxyethyl nitramine (BuNENA). Likewise, the specific impulses of GAP/HMX based compositions with DNEPs as energetic plasticizers were all slightly higher than that of BuNENA. Therefore, these DNEPs (especially DNPBc) exhibit promising potential as candidates for replacement of BuNENA in GAP based propellants.

以3-甲酰胺基-5-氨基-1, 2, 4-1H-三唑为原料,经缩合、环化、酯化、氨化和氧化等反应获得目标化合物3-氰基-5-氨基-1,2,4-1H-三唑（ATCN）,通过优化制约合成工艺的氧化反应体系、反应温度以及反应时间,将收率由文献值37.0%提高至81.6%。采用核磁共振（NMR）、红外吸收（IR）和元素分析等手段表征了结构,通过差示扫描量热法（DSC）和原位红外技术研究ATCN热分解和热裂解特性,并进行热分析动力学计算。结果表明,ATCN第1个热分解峰值温度为163.01℃,对应为氨基和氰基的断裂;第2个热分解峰值温度为244.29℃,对应为三唑环结构的裂解。此外,通过热力学参数计算获得ATCN第1个热分解过程的活化能、活化焓、活化吉布斯自由能和活化熵分别为156.21、153.26、109.80 kJ·mol -1 和103.40 J·K -1 ·mol -1 。

A trifluoromethyl-containing fused triazole-triazine energetic molecule, 3-nitro-7-(trifluoromethyl)-1,2,4-triazolo[5,1-c]-1,2,4-triazin-4-amine (TFX), has been synthesized in three steps from amino guanidine bicarbonate and trifluoroacetic acid. The process was found to be effective, nontoxic, and simple. The X-ray structure analysis of TFX finds that there are inter- and intramolecular hydrogen bonds and π–π interactions in the crystal lattice. TFX with a high density (1.88 g·cm–3) at room temperature, excellent thermal stability (Tp = 300.3 °C), moderate energetic performance, and with insensitivity to mechanical stimulation has potential as heat-resistant energetic materials.

The surface functionalization of graphene oxide (GO) is always attractive in improving certain properties of the polymer. In this study, 3-aminopropyltriethoxysilane (APTES) and 3-mercaptopropyl-trimethoxysilane (SPTES) have been used to make silane functionalized graphene oxides (SiGOs). The APTES-grafted GO (NH-SiGO), SPTES-grafted GO (SH-SiGO) and pure GO have been separately introduced into the nitrocellulose (NC) matrix. The morphology, thermal properties and energetic properties of the prepared nanocomposites (NH-SiGO and SH-SiGO) were investigated comprehensively. It is shown that the presence of GO and SiGOs have different influences on the thermal reactivity of NC with various contents, and NH-SiGO with 0.5 wt% content showed better catalytic performance on the thermal decomposition of NC than others and showed prominently higher efficiency in improving its heat of combustion. Adding 0.5 wt% of NH-SiGO to NC may decrease its decomposition temperature from 202.1 °C to 196.6 °C, and the residue was decreased from 10.61 wt% to 3.95 wt%, respectively. One isoconversional kinetic method was exploited to determine the kinetic parameters of NC and its nanocomposites. It was found that NH-SiGO had a strong catalytic action on the thermal decomposition of NC-based nanocomposites for which the activation energy and the pre-exponential factor were considerably lowered, while SH-SiGO exhibited an inverse effect. The heat of combustion from NC/GO/0.5, NC/NH-SiGO/0.5 and NC/SH-SiGO/0.5 were determined as 11 249.5, 11 675.1 and 11 491.5 J g-1, respectively, which are higher than that of the pure NC (10 908.4 J g-1). From the combustion process of NC/NH-SiGO/0.5, it was shown that the nanocomposite was combusted completely.

2,2-二硝基丙醇分别与乙酸、丙酸、正丁酸经酯化反应,合成2,2-二硝基丙醇乙酸酯、2,2-二硝基丙醇丙酸酯、2,2-二硝基丙醇丁酸酯三种新型偕二硝基酯类增塑剂.利用FTIR、NMR和元素分析等对偕二硝基酯类增塑剂进行了结构表征;考察了催化剂浓硫酸用量、反应物料比及反应时间对产物收率和纯度的影响.结果 表明,2,2-二硝基丙醇乙酸酯较佳合成条件为:浓硫酸用量3％,2,2-二硝基丙醇与乙酸摩尔比为1:1.10,酯化反应时间6 h.测试了所合成的三种新型增塑剂的密度、热分解温度、玻璃化转变温度、感度等性能,并计算了生成焓和溶解度参数.其中2,2-二硝基丙醇乙酸酯的性能如下:密度1.319 g/cm3,溶解度参数20.994 J1/2/cm32,玻璃化转变温度-94.4℃,热分解峰温为254.9℃,生成焓414.5 kJ/mol,摩擦感度4％,撞击感度H50>125.9 cm.

咪唑基含能化合物是目前高能化合物的重要研究方向,而5-氰基-4-氨基咪唑是设计、合成新型咪唑联四唑类高能高氮化合物的关键中间体.以 5-甲酰胺基-4-氨基咪唑(AICON)为原料,经其与三氯氧磷(POCl3)的脱水反应获得了5-氰基-4-氨基咪唑(AICN),通过优化反应体系、反应温度、反应时间以及物料物质的量比,使得AICN的收率＞65%,纯度(HPLC)＞99.5%.此外,采用NMR、IR和元素分析对其进行了结构确证,利用热重分析法研究其热性能.结果表明,AICN的最佳反应条件为以POCl3为脱水剂,n(AICON)∶n(POCl3)=1∶10,反应升温模式为先快速升温至80～85 ℃,维持反应30 min,然后降温至70～75 ℃,维持反应1.0～1.5 h;AICN在40～1000 ℃温度区间存在两个失重过程,对应的热分解温度区间分别为40～400 ℃和400～1000 ℃、热失重分别为19.8%和60.7%、热分解峰温分别为256.5和698.4 ℃,表明其具有良好的热稳定性.

A novel multi‑azido energetic plasticizer bis(3‑azido‑2,2‑bis(azidomethyl) propyl) malonate was designed and synthesized. As the DSC results shown, BAAMPM has a rather low glass transition temperature (-58.3 ℃) and good thermal stability as well as low mechanical sensitivities. Moreover, the viscosity and glass transition temperature of BAAMPM/GAP mixtures are considerably lower than that of GAP, showing that BAAMPM has notable plasticizing effect on GAP.

Recent advances on imidazole bridged azole energetic compounds with the backbones of bisimidazoles， triazolyl imidazoles and tetrazolyl imidazoles were reviewed， the construction strategy for energetic imidazole‑bridged azoles with good coordination of high nitrogen content， high energy and good security was proposed.

With the characteristics of superior thermal stability, lower glass transition temperature, insensitivity and better compatibility with binders, azido plasticizers have vast application prospect in the gun and rocket propellants requiring low vulnerability and low characteristic signal. From the aspects of synthesis, characterization, property and application, recent research progress on azido plasticizers is reviewed in this paper. Then, the existing problems in the research of azido plasticizers are sorted, and some potential development directions on the structure design, synthesis, preparation process, characterization and application are pointed out. This review is expected to benefit the researchers on the synthesis, composition application and property characterization of energetic materials.

This study reports the synthesis and characterization of a novel azido ester plasticizer, 3-azido-2,2-bis(azidomethyl)propyl 2-azidoacetate (ABAMPA), with good yield and high purity. The density, impact sensitivity, friction sensitivity, thermal decomposition temperature and glass transition temperature were determined to be 1.326 g ⋅ cm-3 , 16 J, 324 N, 235.9 °C and -50.4 °C, respectively. The plasticizing effect of ABAMPA on glycidyl azide polymer (GAP) was calculated by molecular dynamics, the solubility parameter difference value was 1.7(J ⋅ cm-3 )0.5 , and the glass transition temperature of GAP was reduced from -35 °C to -43 °C when the weight ratio of ABAMPA and GAP was 50 : 50. The new azido ester exhibits high energy, remarkable thermostability and good compatibility with GAP, which indicates that it would have potential application in explosive and propellant formulations.

The intermediate ethyl nitramine (ENA) and the final product 3,5‑dinitro‑3,5‑diazaheptane (DNDA7) were syntheized starting from 1,3‑diethylurea via the reactions of nitration, hydrolysis and condensation. The yield and purity of ENA is 80.6% and 99.3% while 67.7% and 99.0% for DNDA7, respectively, the overall yield is 54.6%. The structure of DNDA7 was characterized by IR, NMR and elemental analyses. Meanwhile, the reaction conditions for nitration, hydrolysis and condensation were optimized as follows: 20% fuming sulphuric acid and nitric acid were used as the nitrating agents, and the recation temperature was controlled between -5 ℃ to 0 ℃ for nitration reaction; while the hydrolysis reaction was finished in 30 min at 20 ℃; and the molar ratio of ENA and paraformaldehyde is 1∶0.5, the reaction mixture was stirred at 23-25 ℃ for 30 min for condensation reaction. The thermal decomposition properties of DNDA7 and its compatibility with normal energetic materials were studied by using differential scanning calorimetry(DSC). The melting point and thermal decomposition temperature of DNDA7 is determined to be 77.3 ℃ and 260.8 ℃, respectively. DNDA7 performs good compatibility with RDX, basic compatibility with HMX, NQ and GAP, and poor compatibility with NC and FOX‑7. Moreover, the mechanical sensitivities of DNDA7 were tested according to the national standard GJB772A-1997, and it isfound that the impact sensitivity is H50>125.9 cm and the friction sensitivity is 4%.

以三溴新戊醇为原料,经酯化、叠氮化两步反应合成了三叠氮新戊醇乙酸酯(TAP-Ac),总收率78.1％;用红外光谱、核磁共振、元素分析等手段对目标化合物和中间产物结构进行了表征;用差示扫描量热法(DSC)研究了TAP-Ac的热行为,测试了其密度和机械感度;优化了酯化和叠氮化反应条件对收率的影响.结果表明,酯化反应较佳反应条件为:缚酸剂三乙胺与三溴新戊醇摩尔比为1.1∶1.0,乙酸酐与三溴新戊醇的摩尔比为1.5∶1.0,反应时间10h;叠氮化较佳反应条件为:三溴新戊醇乙酸酯与NaN3的摩尔比为1.00∶3.45,反应温度87～90℃,反应时间12h;TAP-Ac的玻璃化转变温度为-73.86℃,热分解温度251.9℃,表明TAP-Ac具有良好的热稳定性;TAP-Ac的密度为1.25g/cm3,撞击感度H50为29.9cm,摩擦感度为8％,表明TAP-Ac是一种钝感、热稳定性良好的新型叠氮增塑剂.

斯蒂芬酸铅和叠氮化铅等传统起爆药含有重金属,对环境污染大,其应用受到了很大的限制.绿色起爆药是一类不含铅、汞等重金属,具有一定安定性且爆轰性能优异的起爆药品种,是当前火工药剂研究领域里的热门课题之一.从绿色起爆药的合成、性能及应用等角度对其近年来的研究进展进行了综述,梳理了绿色起爆药研究的发展方向和趋势,指出今后研究的几点重要方向:努力探索、寻找新的合成线路,并优化其工艺条件,实现绿色起爆药安全化、规模化、稳定化制备;进一步建立、健全绿色起爆药理论设计、性能评估、演示验证等方面的规范和标准;继续开发新型绿色高能起爆药的设计、合成与应用基础研究,进一步改善起爆药的综合性能;设计和选择合适的配体与金属离子以及控制反应条件等因素,对系统研究高氮杂环配位化合物类绿色起爆药的结构与性能具有重要的意义.