间苯三酚的合成及表征

以三硝基甲苯(TNT)为原料,经过氧化、催化氢化、水解等步骤合成间苯三酚。并通过红外、核磁对它的结构进行了确证。考察了氧化剂以及用量、催化剂用量、溶剂、反应温度等对合成间苯三酚的影响。较佳工艺条件:HNO3-KC lO3为氧化剂,氧化剂用量与TNT用量比为2∶1。水-丙酮为催化氢化溶剂,催化剂用量约为反应物的8%,控制温度在60℃,反应2.5 h。水解pH=3~4,反应16~20 h。总收率达到60%,纯度达到98%。     

间苯三酚合成研究进展

间苯三酚是一种重要的中间体,工业合成具有一定的技术难度。本文阐述了国内外间苯三酚合成技术的研究进展,对各种方法的收率、工艺条件与工业化可行性进行了分析。介绍了(异丙)苯法、三硝基甲苯法、氯代苯和苯胺法等具有工业化价值的几种工艺路线,及其应用现状与市场前景。     

间苯三酚的合成研究

本文对间苯三酚的传统生产工艺进行了改进,以KCIO3氧化TNT为TNBA,然后催化加氢,酸性水解制得间苯三酚,反应总收率高于传统工艺。     

间苯三酚合成研究进展

间苯三酚是一种比较昂贵的重要中间体,工业合成具有一定的技术难度.阐述了国内外间苯三酚合成技术的研究进展,包括(异丙)苯法、三硝基甲苯法、氯代苯法、苯胺法等具有工业化价值的几种工艺路线的收率、工艺条件及工业化可行性.＃建议国内企业应该采用较为先进的(异丙)苯法或氯代苯法工艺提高产品质量.     

CL-20/TATB混合物的制备及性能表征

为了提高六硝基六氮杂异伍兹烷(CL-20)的安全性,采用机械混合法和重结晶法分别制备了CL-20/TATB混合物;通过光学显微镜、扫描电子显微镜(SEM)、X-射线衍射(XRD)、差示扫描量热仪(DSC)、感度测试仪对其形貌、晶型、热稳定性、机械感度进行测试分析。结果表明,机械混合后CL-20表面无明显包覆物,而重结晶混合粒子表面有一层致密的黄色薄膜,同时两种混合物中CL-20的晶型仍为ε型,未发生晶型转变;两种混合物的热分解表观活化能较原料CL-20分别提高了17.3、117.36kJ/mol,热爆炸临界温度分别提高了0.12、3.8℃,重结晶混合粒子的热稳定性明显提高;两种混合物的撞击感度(H50)较原料CL-20分别提高了10.4、54.5cm,摩擦感度的临界载荷分别提高了80、60N,表明重结晶混合粒子的机械感度显著降低。     

间苯三酚乙酰基衍生物合成及生物活性研究

以2,4-二乙酰基间苯三酚为基础,通过改变一个酰基碳链的长度,合成了三个间苯三酚乙酰基衍生物,目标化合物经LC-MS进行了确证,室内生测试验结果表明,2-乙酰基-4-丙酰基间苯三酚与2-乙酰基-4-丁酰基间苯三酚对立枯丝核菌、禾谷丝核菌、灰葡萄孢具有明显的抑制作用。     

路易斯酸法合成间苯三酚

以苯胺为原料,经废氢溴酸溴化、脱胺基、甲氧基化、路易斯酸脱甲基四步合成间苯三酚,总收率为67．5％。考察了各种影响因素对合成反应的影响,获得了较佳工艺条件,并对产品后处理作了相应的研究。     

间苯三酚正辛醚的合成

研究了间苯三酚在非质子极性溶剂中,以１８－冠醚－６作催化剂的Ｗｉｌｌｉａｍｓｏｎ反应,轩合成了间苯三酚的单辛基、二辛基和三辛基醚,并对反应条件和产物组成关系进行了讨论。     

声化学胺化法合成TATB

为考察声化学胺化法合成1,3,5-三氨基-2,4,6-三硝基苯(TATB)的应用前景,以1,3,5-三氯-2,4,6-三硝基苯(TCTNB)和氨水为原料,用声化学胺化法合成了TATB,考察了超声波作用方式对TATB粒径的影响。得到的目标产物TATB的质量分数达到97%以上,产率达到90%。采用红外光谱、核磁共振氢谱、质谱、X射线衍射及元素分析鉴定了TATB的结构。DSC测定其分解点为383.8℃;激光粒度仪测试其粒径,由探头式超声波得到的TATB平均粒径为2.46μm,由水槽式超声波得到的TATB平均粒径为14.07μm;氧瓶燃烧法测得TATB中氯质量分数低于0.2%。各项指标均达到了TATB国军标要求。声化学胺化法制备TATB反应条件温和、粒径可控、能耗低、基本排除了安全隐患。     

离子液体中三硝基间苯三酚的绿色合成

为实现2,4,6-三硝基-1,3,5-苯三酚(TNPG)的绿色合成,制备了中性和酸性两类离子液体,将其应用于TNPG的合成,考察了反应温度、硝化剂及其用量对产物收率的影响。实验表明,以Brnsted酸性离子液体[Hmim][HSO4]作为反应溶剂和催化剂,硝酸氧锆为硝化剂,温度60℃时硝化30min后,三硝基间苯三酚的收率可达到42%,离子液体可回收利用。     

无氯TATB的合成及其热分解动力学

为解决传统TATB合成中氯杂质的影响,以间苯三酚为原料,经过五氧化二氮硝化、甲基化和氨气氨化得到TATB,综合收率为92%,用核磁共振光谱、红外光谱和质谱等进行了表征.采用有机溶剂法精制获得高纯度无氯TATB,收率75%.用DSC及TG分析了TATB的热性能,根据Ozawa公式计算出TATB的热分解活化能和指前因子分别为135.28 kJ/mol和2.340×10~9 s~(-1).     

TATB的热分解及其在[Emim]Ac/DMSO溶剂中的热爆炸特性

用DSC-TG研究了TATB的热分解过程。根据升温速率分别为5、10、15、20K/min的DSC和TG-DTG曲线计算了分解反应的活化能(E)、指前因子(A)和120℃时的速率常数(k120),并计算了升温速率为5K/min时,TATB分解峰值温度时的分解反应活化焓、活化熵和活化自由能,用小容量测试法研究了TATB在1-乙基-3-甲基咪唑醋酸盐/二甲基亚砜([Emim]Ac/DMSO)溶剂中的热爆炸特性。结果表明,采用Kissinger法和Ozawa法计算得到TATB分解反应的活化能分别为212.1和212.0kJ/mol,采用Rogers公式和Arrhenius公式计算得到A和k120值分别为5.87×1016s-1和3.87×10-12s-1;升温速率为5K/min条件下,TATB分解峰值温度时的分解反应活化焓、活化熵和活化自由能分别为206kJ/mol、61.42J/(K·mol)和167.39kJ/mol,TATB粉末的临界爆炸温度为336.6℃;TATB在[Emim]Ac/DMSO溶剂中不爆炸。     

由1-硝基蒽醌副产物合成的黄色分散染料的性能研究

本文探讨了由混合硝基蒽醌废渣直接制备黄色分散染料的可利用性,比较了三氯甲烷和N,N-二甲基甲酰胺（DMF）提纯黄色分散染料的热性能和染色性能,并与C.I.分散黄54和C.I.分散橙25复配制备了商品化染料。研究结果表明,DMF提纯的分散黄E-D的热稳定性优于三氯甲烷提纯的分散黄E-T;经提纯的染料都能明显提高染色性能,...     

超细TATB制备方法对粒子结构的影响

采用几种方法制备了超细TATB样品，并对粒子大小、粒径分布、粒子形状、孔容及孔隙分布等进行了表征。结果表明：亚微米TATB样品中有97％以上的粒子粒径小于0．2μm，气流粉碎法和合成法制备的样品粒子形貌呈球形，粒径分布宽，大小不均匀，表面有凹痕；重结晶法制备的样品粒子形貌呈条形，粒子大小比较均匀，粒径分布较窄，冷冻干燥有助于减轻超细粒子间的聚集。     

高能球磨法制备亚微米TATB炸药

高能球磨法是对敏感炸药进行安全细化的有效方法,本文采用高能球磨法对TATB炸药进行微纳化,研究了微纳过程中影响TATB细化效果的因素,包括表面活性剂、水料比、球磨温度、转速和球磨时间;总结了高能球磨法制备超细TATB的操作技巧,如球磨罐的安装、装料量的控制、磨腔内物料降温和磨球上物料的冲洗。上述研究和总结为安全高效利用高能球磨机制备超细炸药进行了有益尝试与探索,优化条件下得到了亚微米级超细TATB炸药。     

Preparation and Characterization of Nano‐TATB Explosive

Nano‐TATB was prepared by solvent/nonsolvent recrystallization with concentrated sulfuric acid as solvent and water as nonsolvent. Transmission Electron Microscopy (TEM) and Atomic Force Microscopy (AFM) were used to characterize the appearance and the size of the particles. The results revealed that nano‐TATB particles have the shape of spheres or ellipsoids with a size of about 60 nm. Due to their small diameter and high surface energy, the particles tended to agglomerate. By using X‐ray powder diffraction (XRD), broadening of diffraction peaks and decreasing intensity were observed, when the particle sizes decreases to the nanometer size range. The corrected average particle size of nano‐TATB was estimated using the Scherrer equation and the size ranged from 27 nm to 41 nm. Furthermore, the specific surface area and pore diameter of nano‐TATB were determined by BET method. The values were 22 m²/g and 1.7 nm respectively. Thermogravimetric (TG) and Differential Scanning Calorimetric (DSC) curves revealed that thermal decomposition of nano‐TATB occurs in the range of 356.5 °C–376.5 °C and its weight loss takes place at about 230 °C. Furthermore, a slight increase in the weight loss was observed for nano‐TATB in comparison with micro‐TATB.     

Towards a heat- and mass-balanced kinetic model of TATB decomposition

TATB (1,3,5-triamino-2,4,6-trinitrobenzene) was thermally degraded by two small-scale analytical methods – simultaneous differential scanning calorimetry and thermogravimetric analysis (SDT) and a hot-stage microscope with Fourier Transform Infrared (FTIR) analysis capabilities. SDT used ramped heating, isothermal soaking, and thermal pretreatment at various conditions. The heat flow and mass loss were monitored during various treatment conditions to derive chemical decomposition kinetics and Arrhenius parameters. FTIR experiments used isothermal heating, and changes were monitored spectroscopically. Solid samples generated at specific conditions were collected from both methods and were analyzed by DMSO extraction followed by chemical speciation by optical and mass spectrometric methods. Characterization provided the following reaction insights: 1. TATB decreases in a sigmoidal pattern in isothermally heated samples. Other soluble products gradually increase in concentration and then abruptly decline in concentration during the second exotherm, such as diamino-dinitro-benzofurazan and amino-nitro-benzodifurazan. 2. FTIR showed gradual changes in the amino and nitro functionality, shifting positions and decreasing intensity for the first 40 min. Then the solid gradually appeared more like an amorphous C with N incorporated, similar to previous studies on thermally degraded TATB-type materials. 3. Extracted residues (DMSO-soluble components removed) examined by FTIR showed an abrupt change in chemical composition between 40- and 45-min isothermal treatment, indicating early forming solids are different than later forming residues. 4. A reliable mass- and energy-balanced global reaction network must include at least two autocatalytic reactions, either in parallel or series, and at least one must have an explicit initiation reaction having a low activation energy.     

TATB/HMX共晶炸药的制备及性能研究

采用溶剂/非溶剂法,在超声辅助的情况下,制备了TATB/HMX共晶炸药;探究了TATB/HMX共晶技术的影响因素;计算了TATB/HMX共晶炸药的理论密度和理论爆速;采用扫描电子显微镜(SEM)、X射线衍射仪(XRD)和差示扫描热量法(DSC)对其进行表征和热分析,并测试了其撞击感度。结果表明,制备TATB/HMX共晶的最佳工艺条件为:以[Emim]Ac/DMSO为复合溶剂,TATB和HMX投料比(摩尔比)为3∶7,温度为80℃,搅拌速率为500r/min;与原料相比,TATB/HMX共晶分子在结构上发生改变;TATB/HMX共晶炸药颗粒大小约为2μm,形貌为六边形晶体;共晶炸药的热安定性优于原料HMX,其特性落高比原料HMX高74cm,撞击感度明显降低;理论密度为1.891g/cm~3,理论爆速为8.758km/s,表明其爆炸性能良好。     

Comparative analysis of sublimation and thermal decomposition of TATB

This experimental study investigated the effects of confinement, starting mass, and heating rate on TATB thermal decomposition and sublimation using a combined Thermo-Gravimetric Analyzer and Differential Scanning Calorimetry (TGA/DSC) instrument. The confinement of volatile products was varied using different pinhole sizes with TGA/DSC pans. The measurements showed the open pan experiments without lids/pinholes resulted in complete sublimation of TATB between 320 °C and 360 °C. The heat of sublimation was determined to be 176 kJ/mol (42 kcal /mol), consistent with literature data obtained from other experimental techniques. The use of pinholes suppressed the sublimation of TATB such that the decrease in pinhole size resulted in 1) an increase in the enthalpy of reaction and an increase in the amount of carbonaceous material remaining at the end of decomposition, and 2) convergence of the two peak temperatures corresponding to maximum heat flow and maximum weight loss. Also, a transition from a two-exotherm thermal decomposition behavior towards a single-exotherm occurred as the pinhole size was decreased for a given starting mass or as the starting mass was increased for a given pinhole size. These results indicate the kinetics of TATB sublimation, TATB thermal decomposition, and gas diffusion out of a TGA/DSC pan can all compete and result in significantly different enthalpies, amounts of remaining materials, and peak temperatures depending on the pinhole size and starting mass used in the measurements. The results also indicate precise control of process variables (pinhole size, starting mass, and heating rate) in TGA/DSC measurements is required for thermal safety assessment of explosives.