相转移催化法合成BBMO和BAMO

以1，1，1-三溴甲基-1-羟甲基甲烷为原料、水和甲苯为反应溶剂、季铵盐为相转移催化剂，在NaOH的作用下经关环反应合成3，3-双溴甲基氧杂环丁烷（BBM0）；以季铵盐为相转移催化剂，BBMO在水相介质中经叠氮基取代反应制备出3，3-双叠氮甲基氧杂环丁烷（BAM0）；用红外、核磁表征产品结构，高效液相色谱分析产品纯度。结果表明，BBMO收率与纯度分别为81％和97．2％；BAM0收率与纯度分别为80．9oA和98．37％。用相转移催化法制备BBMO和BAMO具有收率高、纯度高、安全性好等特点。     

相转移催化法合成BBMO和BAMO

以1,1,1-三溴甲基-1-羟甲基甲烷为原料、水和甲苯为反应溶剂、季铵盐为相转移催化剂,在NaOH的作用下经关环反应合成3,3-双溴甲基氧杂环丁烷(BBMO);以季铵盐为相转移催化剂,BBMO在水相介质中经叠氮基取代反应制备出3,3-双叠氮甲基氧杂环丁烷(BAMO);用红外、核磁表征产品结构,高效液相色谱分析产品纯度.结果表明,BBMO收率与纯度分别为81%和97.2%;BAMO收率与纯度分别为80.9%和98.37%.用相转移催化法制备BBMO和BAMO具有收率高、纯度高、安全性好等特点.     

3-叠氮甲基-3-甲基氧丁环的合成

以三羟甲基乙烷与碳酸二乙酯为原料,经环化反应合成了3-羟甲基-3-甲基氧丁环(HMM O)。在低温下,HMM O与对甲苯磺酰氯反应生成3-磺酸酯甲基-3-甲基氧丁环(M TM O)。M TM O和叠氮化钠发生叠氮化反应形成叠氮单体3-叠氮甲基-3-甲基氧丁环(AMM O)。三步反应收率分别为76%,96%,85%。用核磁、红外、元素分析和DSC表征了化合物的结构与性能。结构鉴定表明为目标化合物AMM O。     

3-硝酸酯甲基-3-甲基氧杂环丁烷的合成及表征

为发展硝酸酯聚醚黏结剂,以3-羟甲基-3-甲基氧杂环丁烷（HMMO）为底物,N2O5为硝化剂,制备了一种含能单体3-硝酸酯甲基-3甲基氧杂环丁烷（NIMMO）。讨论了N2O5与HMMO的摩尔比及反应温度对选择性硝化的影响。确定了最佳反应条件：N2O5与HMMO的摩尔比为（1．0～1.1）：1．0,温度为-15～-10℃,滴加完毕后待温度下降时立即中和终止反应。通过红外、核磁及元素分析对产品进行结构表征,表明是目标化合物,差热分析表明NIMMO的热稳定性较好。     

3-溴甲基-3-甲基氧杂环丁烷均聚物的合成及表征

以1,4-丁二醇(BDO)为引发剂,三氟化硼乙醚络合物(BF3·Et2O)为催化剂,3-溴甲基-3-甲基氧杂环丁烷(BrMMO)为单体,CH2Cl2为溶剂,按阳离子开环聚合机理,合成出有机黏合剂3-溴甲基-3-甲基氧杂环丁烷均聚物(PBrMMO).研究了低温条件下单体转化率随时间的变化情况,得出BrMMO转化率-时间曲线,考察了催化剂用量和反应体系温度对可控聚合的影响,确定出BrMMO可控聚合的最佳条件:BF3·Et2O与BDO的摩尔比为0.5∶1.0,0℃下加入单体并熟化3d.用IR、1HNMR、DSC及TGA对最终产物的结构与性能进行了表征.     

3-叠氮甲基-3-甲基氧杂环丁烷与四氢呋喃共聚醚的合成与表征

以1,4-丁二醇(BDO)为引发剂,三氟化硼·乙醚(BF3·Et2O)为催化剂,使3-叠氮甲基-3-甲基氧杂环丁烷(AMMO)与四氢呋喃进行本体法阳离子开环聚合,得到3-叠氮甲基-3-甲基氧杂环丁烷与四氢呋喃的共聚醚(PAT).通过红外光谱、核磁共振氢谱、碳谱和凝胶渗透色谱对共聚醚进行表征.结果表明,合成的共聚醚中两种不同结构单元的摩尔比与投料比基本吻合,共聚醚的相对分子质量可控、分布较窄.差热扫描量热法测得PAT的玻璃化转变温度为-59.2℃,分解峰温为264.1℃,表明其具有良好的低温性能和热稳定性.     

双官能团氧杂环丁烷活性单体的合成及固化性能的研究

以3-乙基-3-羟甲基氧杂环丁烷为原料,分别与对二溴苄,联苯二氯苄和双[4-(2-羟基乙氧基)苯基]丙烷合成具有双氧杂环丁烷官能团的活性稀释剂OXT121,OXBP,OXBPA单体。在光源为高压汞灯,波长为365 nm,测试时间为180 s的条件下,用GR61硫鎓盐作光引发剂,对OXT121,OXBP,OXBPA三种单体进行了实时红外转化率测试;对E-51环氧树脂黏度稀释效应进行了测定。结果表明,OXT121,OXBP,OXBPA三种活性单体具有良好的转化率,且能有效降低E-51环氧树脂黏度,是一类优良的UV阳离子活性稀释剂。     

3-硝酸酯甲基-3-乙基氧杂环丁烷的合成及表征

以三羟甲基丙烷和碳酸二乙酯为原料,经环化、硝化两步反应合成出了3-硝酸酯甲基-3-乙基氧杂环丁烷(NIMEO),硝化反应的收率为75.1％,产品质量分数为98.8％.通过红外光谱、核磁共振氢谱及元素分析对产品的结构进行了表征,表明为目标化合物.考察了反应条件对产品收率的影响,确定了最佳的硝化条件:硝酸/醋酐为硝化剂,硝...     

含能黏合剂PAMMO的间接法合成

以3-溴甲基-3-甲基氧杂环丁烷(BrMMO)为单体,按阳离子开环聚合机理,先合成出3-溴甲基-3-甲基氧杂环丁烷均聚物(PBrMMO),接着在偶极非质子溶剂中对其进行叠氮化,最终合成出含能黏合剂3-叠氮甲基-3-甲基氧杂环丁烷均聚物(PAMMO)。着重研究了BrMMO聚合过程中催化剂用量和反应体系温度对聚合的影响,确定出BrMMO聚合的最佳条件为:n(BF3.OEt2):n(BDO)=0.50:1.00,0℃下加入单体,通过红外光谱确定出叠氮化反应的完成时间。用红外光谱(IR)、核磁共振(1H-NMR)、热重分析(TGA)和差示扫描量热法(DSC)对产品进行了表征。     

含能黏合剂PAMMO的问接法合成

以3-溴甲基-3-甲基氧杂环丁烷(BrMMO)为单体,按阳离子开环聚合机理,先合成出3-溴甲基-3-甲基氧杂环丁烷均聚物(PBrMMO),接着在偶极非质子溶剂中对其进行叠氮化,最终合成出含能黏合剂3-叠氮甲基-3-甲基氧杂环丁烷均聚物(PAMMO).着重研究了BrMMO聚合过程中催化剂用量和反应体系温度对聚合的影响,确定出BrMMO聚合的最佳条件为:n(BF3OEt2):n(BDO)=0.50:1.00.0℃下加入单体,通过红外光谱确定出叠氮化反应的完成时间.用红外光谱(IR)、核磁共振(1H-NMR)、热重分析(TGA)和差示扫描量热法(DSC)对产品进行了表征.     

3,3-双叠氮甲基氧丁环及其均聚物的合成与性能

以1,1,1-三溴甲基-1-羟甲基甲烷为原料,无水乙醇为溶剂,在NaOH的作用下经关环反应合成了3,3-二溴甲基氧丁环(BBMO)。BBMO经叠氮基取代反应制备出3,3-二叠氮甲基氧丁环(BAMO)。BAMO单体经阳离子开环聚合即可制备出固态含能黏合剂PBAMO。用核磁、红外、DSC和GPC表征了聚合物的结构,测试了PBAMO的理化性质。结果表明,PBAMO具有感度较低．熔融温度适中,熔融黏度较低等特点,可以作为含能热塑性弹性体的硬段成分。     

1-甲基-5-硝亚胺基四唑及其盐的合成与表征

以甲胺和叠氮化氰为原料经缩合作用合成了1-甲基-5-氨基四唑,在发烟硝酸最佳用量为5 mL、室温和反应时间20h条件下,经硝化得到1-甲基-5-硝亚胺基四唑.通过1-甲基-5-硝亚胺基四唑作阴离子和5种高氮含能阳离子的反应,分别合成出1-甲基-5-硝亚胺基四唑铵盐、1-甲基-5-硝亚胺基四唑肼盐、1-甲基-5-硝亚胺基...     

Energetics of AMMO

The thermal decomposition process and combustion wave structure of azide polymer were studied to determine the parameters which control the burning rate. The azide polymer studied was 3-azidomethyl-3-methyl oxetane (AMMO) which contains energetic –N₃ groups. From the experiments, it was found that the thermal decomposition process of AMMO consists of a two-stage weight loss process: the first-stage corresponds to an exothermic reaction which is caused by the scission of N-N₂ bond, and the second-stage corresponds to the decomposition of the remaining fragments. The burning rate of AMMO is approximately 50% of the burning rate of GAP propellant and is as high as that of conventional double base propellant. The heat feedback from gas phase to the burning surface increase with increasing pressure. The burning surface temperature and the heat of reaction at the surface decrease with increasing pressure.     

Thermal characteristics of energetic polymers based on tetrahydrofuran and oxetane derivatives

Thermal characteristics and decomposition behaviors of energetic polymers based on oxetane derivatives, 3,3'-bis(azidomethyl)oxetane (BAMO), 3-azidomethyl-3'-methyloxetane (AMMO), 3-nitratomethyl-3'-methyloxetane (NMMO), and 3,3'-bis(ethoxymethyl)oxetane (BEMO), were studied by means of differential scanning calorimeter (DSC) and thermogravimetric analyzer (TGA). These polymers were found to exhibit low glass transition and large decomposition onthalpies which were brought about by the attached azide (? N₃) and nitrato (? ONO₂) groups. The decomposition enthalpies depended on the types and contents of the energetic substituents. The NMMO-based polymers exhibited relatively higher decomposition enthalpies and less thermal stability than the others. Furthermore, the thermal stability of the polymers was further improved by partial curing treatment. These results reveal that these polymers are potentially useful for application in energetic propellant binders. © 1995 John Wiley & Sons, Inc.     

一种新型咔唑席夫碱的合成及对Fe~(3+)荧光识别研究

以9-氨基咔唑与2-羟基-1-萘甲醛为原料,设计合成了一种新型咔唑类席夫碱化合物。通过核磁共振光谱、质谱、红外光谱和元素分析对其结构进行表征,利用荧光光谱研究了目标化合物对不同金属离子的荧光识别性能,采用质谱和密度泛函理论(DFT)分析其与Fe~(3+)结合作用模式。结果表明,目标化合物通过荧光猝灭可选择性识别Fe~(3+),原因是与Fe~(3+)配位后引发了分子内的光诱导电子转移过程有关。     

Synthesis and Characterization of Deuterated Glycidyl Azide Polymer (GAP)

Decomposition mechanisms of propellants are of great interest in understanding performance issues of chemical propulsion systems. The characterization of physico‐chemical properties of glycidyl azide polymer (GAP), specifically deuterated analogs, was investigated in this study. The purpose of this new approach is to identify the key steps in thermal decomposition mechanism of GAP. The present work shows that the use of deuterated GAP is a good method to study the decomposition pathway of energetic polymers. The polymerization process was successful, but was nevertheless affected by the use of the isotopic monomer since the resulting polymers had a slightly lower molecular weight. The chemical characterization of the deuterated GAPs by NMR and FTIR confirm the structure of these new polymers. The TGA analyses show a larger weight loss during the first step of decomposition for labeled GAP suggesting that molecular nitrogen and heavier compounds are produced simultaneously.     

Potential Energetic Plasticizers on the Basis of 2,2‐Dinitropropane‐1,3‐diol and 2,2‐Bis(azidomethyl)propane‐1,3‐diol

Different carboxylic acid derivatives of 2,2‐dinitropropane‐1,3‐diol (DNPD) and 2,2‐bis(azidomethyl)propane‐1,3‐diol (BAMP) were synthesized to investigate their suitability as energetic plasticizers. The syntheses were carried out using acyl chlorides of acetic, propionic, and butyric acid. The obtained products were characterized by elemental analysis, NMR, and IR spectroscopy. The energetic properties of the synthesized compounds were calculated on the basis of the computed heats of formation at the CBS‐4M level of theory using the EXPLO5 version 6.02 computer code. Investigations of physical stabilities were carried out using BAM drop hammer and friction tester. Low and high temperature behavior was determined by differential scanning calorimetry (DSC). The energetic and physical properties of the synthesized compounds were compared to the literature known energetic plasticizers N‐butyl nitratoethylnitramine (BuNENA) and diethylene glycol bis(azidoacetate) ester (DEGBAA). For analyzing the plasticizing abilities, mixtures of glycidyl azide polymer (GAP) and poly(3‐nitratomethyl‐3‐methyloxetan) (polyNIMMO) were prepared with both propionyl based compounds in different ratios and investigated regarding their glass transition temperatures and viscosity. Both compounds showed plasticizing effects in the range of BuNENA.     

2,5-二羟基对苯二甲酸的合成研究

PIPD纤维是一种新型液晶芳杂环聚合物纤维,它是由2,3,5,6-四氨基吡啶(TAP)和2,5-二羟基对苯二甲酸(DHTA)两种单体制得,研制的目的是合成单体DHTA,并对其进行分析表征.用对二甲苯为溶剂、对苯二酚和碱金属碳酸盐及碱金属碳酸氢盐作为原料,在N2的气氛和一定压力下可制备出2,5-二羟基对苯二甲酸,通过HPLC、FT-IR、DSC、元素分析和核磁等对产物结构和纯度进行表征,发现产物结构正确,且纯度可达99.5%.实验结果表明,该工艺路线可行,产物纯度高,重复性好,是一个工艺简便、成本低的好方法.