N,N-二甲基-2-叠氮乙胺(DMAZ)具有无毒、密度大、生成焓高、燃速高、燃烧产物洁净等优点,是可替代肼类推进剂的新型液体燃料.综述了液体燃料DMAZ的合成、性能及应用研究进展.建议:加快DMAZ配方的应用研究,推动该材料在液体推进剂中的应用;开发DMAZ合成新工艺,解决目前几种工艺存在的收率低、安全风险高、工艺复杂的问题.

为了研究硝仿系炸药的合成,以4,6-二羟基嘧啶为硝化原料制备硝仿,然后合成4,4,4-三硝基丁酸-2,2,2-三硝基乙酯(TNETB);采用红外光谱、核磁共振波谱、质谱以及元素分析等对TNETB进行了结构表征;考察了物料比、反应温度和反应时间对产物收率的影响,以甲醇为溶剂培养了TNETB单晶,并采用X-射线单晶衍射进行晶体结构测定.结果表明,制备TNETB的最佳反应条件为:硝仿、甲醛水溶液和丙烯酸的摩尔比为4.2:1.2:1.0,无需溶剂,缩合反应时间45 min,反应温度为25℃;加成反应时间为60 min,反应温度为50℃;酯化反应时间为60 min,反应温度为50℃;TNETB的收率为40.7％,纯度为98.7％;TNETB晶体属于单斜晶系,P2(1)/n空间群,晶体学参数为:a=5.8799(13)?,b=21.801(5)?,c=11.220(2)?,V=1434.1(5)?3,Z=4,DC=1.789g/cm3,μ=0.180mm-1,F(000)=784,R1=0.0960,ωR2=0.2857;TNETB分子间的氢键和范德华力降低了硝仿基团的引入对分子稳定性和安全性的影响,表明TNETB具有较高的安全性.

With diethylene glycol (DEG) and triethylene glycol (TEG) as starting materials, novel energetic plasticizers 1,5‑diazido‑3‑oxopentane (AZDEGDN) and 1,8‑diazido‑3,6‑dioxooctane (AZTEGDN) were synthesized via nitration and azidation reaction. The conditions of azidation reaction were optimized. And the structures were characterized by infrared spectra, magnetic resonance spectra and element analysis. Results show that the optimal reaction conditions for the synthesis of AZDEGDN are the molar ratio of sodium azide and DEGDN of 2.7∶1, the reaction temperature of 80 ℃,and the reaction time of 8 h, under which the yield of AZDEGDN is 96.4% and the purity is 99.1%.The optimal reaction conditions for the synthesis of AZTEGDN are the molar ratio of sodium azide and TEGDN of 2.5∶1, the reaction temperature of 75 ℃, and the reaction time of 8 h, under which the yield of AZTEGDN is 96% and the purity is 99.2%. In addition, the enthalpy of formation, the decomposition temperature, the friction sensitivity and impact sensitivity of AZDEGDN are 912.5 kJ·mol-1, 249.3 ℃, 0% and 64.6 cm, respectively; while the main properties of AZTEGDN are 898.1 kJ·mol-1, 256.1 ℃, 0% and 151.4 cm, respectively. However, both of their glass transition temperatures are less than -100 ℃.

键合剂是改善黑索金(RDX)、奥克托金(HMX)等硝胺和氧化剂填料与黏合剂间界面作用的关键功能材料,也是提高推进剂力学性能的有效、方便、实用的策略.综述复合推进剂中硼酸酯(BEBA)与中性聚合物(NPBA)等键合剂的研究进展,归纳了键合剂的作用机理,梳理了当前和未来高性能推进剂用键合剂的发展动向,针对不同的黏合剂体系和新的固化方式等发展趋势,设计具有多种功能基团的键合剂结构,积极开发可同时与硝胺、氧化剂及黏合剂相匹配的键合剂,进一步完善补充键合机理,以满足高新武器系统对高力学性能推进剂的需求.

以氰基乙酸甲酯为原料,经过取代、环化成盐、水解制备3-氨基呋咱-4-羧酸.利用红外光谱、核磁共振波谱、元素分析及质谱确证了产物结构,并考察了物料比、反应温度、反应时间和溶剂用量对环化成盐反应的影响及反应溶剂、pH、温度对酸化反应的影响,发现增加氢氧化钾用量、提高反应温度、降低体系pH有利于目标物收率提高.得到的最佳环化成盐反应条件为:n(盐酸羟胺):n(氢氧化钾):n(2-氰基-2-肟基乙酸甲酯)=1:2:1,缩合温度25℃,缩合时间2 h,环化温度80℃,环化时间2 h,溶剂水50 mL;最佳酸化反应条件为:溶剂水30 mL,pH≤1,反应温度5℃,环化成盐反应和酸化反应的总收率为79.73％,高于文献报道的64％.

以二苯胺为原料,二甲氨基吡啶为催化剂,与固体光气经过缩合反应得到二苯基氨基甲酰氯,再与甲胺反应,合成安定剂N'-甲基-N,N-二苯脲(AK-Ⅱ).通过红外分析、核磁共振、元素分析等手段鉴定了其结构.讨论了反应介质、时间、催化剂对一次缩合收率的影响,反应介质乙醚,时间4h,催化剂二甲氨基吡啶,收率95％.并用真空安定性法测试了AK-Ⅱ与推进剂主要组分的相容性.结果表明,AK-Ⅱ与吸收药(NC+ NG)、硝基胍(NQ)、黑索今(RDX)、铝粉(Al)、高氯酸铵(AP)、端羟基聚丁二烯(HTPB)、奥克托今(HMX)、甲苯二异氰酸酯(TDI)、三醋精(TA)、含能粘合剂(BAMO-THF)、固化剂(N-100)的相容性良好.

利用微反应技术,分别以1,2-丙二醇、三羟甲基乙烷为原料,硝硫混酸为硝化剂,合成了1,2-丙二醇二硝酸酯(PGDN)和三羟甲基乙烷三硝酸酯(TMETN);采用红外光谱、核磁共振等对其结构进行了表征,同时优化了微反应器硝化反应条件.结果表明,TMETN和PGDN结构与间歇式合成产物一致,合成TMETN的较佳硝化温度为17～20℃,硝酸与三羟甲基乙烷的最佳摩尔比为5.6:1.0,收率达90.0％ 以上,纯度达98.5％;合成PGDN的较佳反应温度为20～22℃,硝酸与1,2-丙二醇的摩尔比为2.7:1.0.该工艺具有反应温度范围宽、硝酸用量少和收率高等优点.

以氯代乙酸乙酯为原料,经叠氮化、水解、酯化等反应合成了新型含能增塑剂1,3-二叠氮基-2-叠氮乙酸丙酯(PCPAA).采用红外光谱、核磁共振及元素分析对其结构进行了鉴定.优化了酯化反应条件.研究了影响酯化反应收率的因素,包括1,3-二叠氮丙醇/叠氮乙酸(DAG/AAE)摩尔比、催化剂和反应时间.采用DSC和感度测试仪测定了PCPAA的热性能,冲击感度和摩擦感度.结果表明,在确定的最佳酯化反应条件(酯化反应∶DAG/AAE摩尔比为1.4,催化剂为硫酸,反应时间为9h下,收率为71.4％,纯度为99.1％.对PCPAA,ρ=1.32 g·cm-3,玻璃化温度Tg(DSC) ＜-80℃、分解峰温Tp(DSC)=240.7℃,摩擦感度为0％,撞击感度为37.2cm.

以吡唑为原料,经N-硝化、热重排、C-硝化等反应合成了3,4-二硝基吡唑(DNP).进行了DNP的放大工艺研究,优化了硝化工艺条件,考察了C-硝化的工艺稳定性及重结晶溶剂苯甲腈的循环利用.研究发现:DNP较佳反应温度为55～57℃,反应时间45 min,收率86.8％;DNP的放大硝化工艺具有较好的稳定性,重结晶溶剂可以循环利用5次以上,重结晶纯度99％以上.该放大合成工艺得到的DNP具有良好的物理化学性能,有望应用于混合炸药的研制.

三硝基乙基氮杂环类衍生物具有含氧量高、密度高等优点,是一类重要的含能材料.本文综述了三硝基乙基氮杂环类衍生物研究进展,重点阐述了该类化合物的合成、性能及应用研究进展,进一步探讨了三硝基乙基氮杂环类衍生物在高能炸药、推进剂等含能材料领域中的应用前景.

1,3-di (azido-acetoxy)-2-ethyl-2-nitropropane (ENPEA) was synthesized using 2-ethyl-2-nitro-1,3-Pro-panediol as raw material, via two-step reactions of esterification and azidonation at a total yield of 83%. Its structure was identified by IR, NMR and elemental analysis. Influencing factors of azidonation were studied. The optimum conditions of the reactions are:n(NaN3)︰n(ENPE) =2. 2︰1. 0, 13%-20% of the total volume of acetone-H2O and reaction time of 2 h. Some physicochemical properties of ENPEA were obtained by tests as the glass transition temperature of -43. 4℃, the decomposition temperature of 252. 4℃, the density of 1. 34g/cm3, H50 of 120. 2 cm (2 kg drop hammer), and the friction sensitivity of 4% (66° oscillation angle).

Recycling of exercise torpedo will produce a large amount of fuel containing seawater.To ensure the safety of processing of seawater contaminated OTTO-Ⅱ,DSC and HPLC was used to study the composition and stability after mixing of pure OTTO-Ⅱ with seawater at different temperatures and durations.Results show that DBS decreases with the increase of mixing temperature,which may be related to the saponification of DBS at high temperature.Thermal decomposition performance of OTTO-Ⅱ is not obviously affected by seawater.This research may provide technical and safety reference for the separation and recovery of fuel containing seawater.

Two kinds of bonding agent based on"click chemistry" ( BA-2&BA-7) were synthesized and explored for applica-tion in the solid rocket propellants cured by triazole-crosslinked curing system. Compatibility between BAs and ADN was investiga-ted by DSC and it turns out to be compatible with ADN. The reaction capability between BAs and GAP was investigated by means of DSC and FT-IR. The results show that the BAs can react with GAP. Besides, the surface properties have shown that the BAs can be adsorbed on the surface of ADN, thus the synthesized BAs are potentially useful in the triazole-crosslinked curing system.

An energetic plasticizer 4,4,4-trinitrobutyric acid 2-azido-1-azidomethyl-ethyl ester(DPTB) was synthesized via esterifi-cation reaction from 4,4,4-trinitrobutyric acid(TNB) and 1,3-diazido-propan-2-ol(DAG),in which,TNB was prepared via nitration-hydrolysis and addition reaction using 4,6-dihydropyrimidine as raw material,and DAG was prepared via azidation by 1,3-dichloro-propan-2-ol as raw material.The structure of DPTB was characterized by IR,NMR and elemental analyses.In synthesis,traditional esterification method was replaced by dicyclohexylcarbodiimide (DCC)/dimethylaminopyridinium p-toluenesulfonate (DPTS) catalytic esterification method.The effects of material ratio,reaction temperature,reaction time and solvent dosage on the esterification reaction were investigated.The thermal decomposition properties of DPTB were studied by thermogravimetry (TG) and differential scanning calorimetry(DSC).Results shw that replacing traditional esterification method with DCC/DPTS catalytic esterification method makes the yield of DPTB promote from 1 7.9％ to 44.9％.There are two exothermic peaks at 215 ℃ and 230 ℃ on DSC curve of DPTB.Its TG curve can be divided into two stages:first-stage is from147 ℃ to 220 ℃ accompanied with 76.68％ mass loss;second-sstage is from 220 ℃ to 351 ℃ accompanied with 1 5.23％ mass loss and the total mass loss from start to the end of decomposition reaction is 91.19％.

以二乙醇-N-硝胺二硝酸酯(DINA)为起始原料,经过叠氮化、萃取、分离、纯化等工序合成出含能增塑剂3-硝基-5-叠氮基-3-氮杂戊醇硝酸酯(PNAN);通过红外光谱、核磁共振及元素分析对目标化合物进行了表征,并测试了其热安定性和机械感度.结果表明,PNAN合成的最佳工艺条件为:叠氮化钠(NaN3)与DINA的摩尔比为1.2∶1.0、反应时间为3h、反应温度为75～80℃;测得PNAN的密度为1.46 g/cm3,热分解温度为172℃,玻璃化转变温度为-41℃,摩擦感度为12％,撞击感度为56％;得出PNAN是一种热稳定好、感度适中的含能材料,有望作为含能增塑剂应用于固体推进剂和发射药中.

A new method for the synthesis of 1,4,5,8-tetranitro-1,4,5,8-tetraazabicyclo[4. 4. 0]decalin (TNAD) was studied. This compound was prepared from the raw material 1,4,5,8- tetraazabicyclo[4. 4. 0]decalin (THAD) via salt-forming reaction and nitrolysis. The total yield could reach as high as 90%, and the purity is 98. 7%. Structure of the product was characterized by IR, 1 H NMR and elemental analysis. The effects of nitrification system, reactant ratio, reac-tion temperature and reaction time on the yield have been investigated. Results show that the optimum reaction conditions of the reaction are determined as:n (THAD.4HNO3)︰n(98%HNO3)︰n (AC2O) = 1︰24︰15. Meanwhile, the best reaction temperature is 25 ℃ and the best reaction time is 2 h.

为了降低星型含能热塑性弹性体(SETPE)的玻璃化温度,提高其柔顺性,以单官能度PBAMO (UPBAMO)为硬段,数均分子量(Mn)为4000 ～6000的聚四氢呋喃改性三官能度聚叠氮缩水甘油醚(APP)为软段,2,4-甲苯二异氰酸酯为偶联剂,通过预聚体偶联法合成出聚四氢呋喃改性PBAMO/APP基AnB星型ETPE(TSETPE).确定了UPBAMO封端反应时间为2h的优化合成条件.采用红外、核磁共振、凝胶渗透色谱和力学性能测试对其进行了表征.所合成的TSETPE Mn为15000 ～19000,与Mn相近的SETPE相比,TSETPE的玻璃化温度由-16.9℃下降到-24.3℃,常温延伸率则由44.5％提升到652％ ～919％.应用研究表明TSETPE与黑索今、铝粉、硝化甘油等火炸药常用材料均具有良好的相容性,以其为粘合剂制备的TSETPE基熔铸高聚物粘结炸药(PBX)具有高能特性,爆热可达7411J·g-1.

利用4-硝基咪唑和高氯酸水溶液反应制得4-硝基咪唑高氯酸盐,培养出该配合物的单晶.通过元素分析、红外光谱、X射线单晶衍射等方法对该配合物结构进行了表征.结果表明,该晶体属于正交晶系,空间群为Pca21,晶胞参数a=1.069 4(6) nm,b=0.656 2(4)nm,c=1.046 6(6) nm,β=90.00°,V=0.734 4(7) nm3,Dc=1.931 g/cm3,Z=4,F(000)=432,R1=0.029 2,wR2=0.049 5.该化合物热分解温度为175℃,且对撞击作用、摩擦作用、火焰作用均钝感.

用N-硝基二乙醇胺二硝酸酯(DINA)和叠氮化钠为原料,在二甲基亚砜中反应合成了一种分子中含-N-NO2,-N3,-ONO2基团的新型含能增塑剂,3-硝基-5-叠氮基-3-氮杂戊醇硝酸酯(PNAN)(粗品).粗产品经硅胶柱色谱分离净化.所得纯产品的纯度为98.60％.纯产品的结构用IR、1H NMR及元素分析表征.测试得到PNAN的密度为1.46 g· cm-3,热分解温度为172 ℃,玻璃化转变温度为-41℃,粘度为19.5 mPa·s,摩擦感度为12％,撞击感度为56％.

Triazidotriacetin( TAA)was synthesized via esterification and azidonation using propanetriol as raw material. The over-all yield was 84. 1%. The structures of intermediates and target compound were characterized by IR,NMR and elemental analysis. The factors affecting esterification and azidonation reactions were discussed. Results show that the optimum conditions of azidona-tion reaction are determined as:the dosage of NaN3 is 1.10 times of theoretical value,i. e. nexp ∶ ntheo=1.10(molar ratio),the dosage of water is 5% ~25% of the total volume of acetone-water mixed solvent,and the reaction time is 10 h. The yield of TAA is 95. 0% and its purity more than 96. 8%.