In order to solve the problems of long rearrangement time,high toxicity of rearrangement reagents and easy subli-mation of N-nitropyrazole(N-NP)in the synthesis of 3-nitropyrazole(3-NP),N-nitropyrazole was used as raw material to pre-pare 3-NP by the hydrothermal method using xylene as the rearrangement solvent,and the structures were characterized by mi-croscope and IR spectrum.The reaction temperature,reaction time,filling degree and other factors were optimized.The re-sults show that the optimal reaction conditions are as follows:reaction temperature of 180℃,holding time of 3 h,filling de-gree of 15％,and the yield of 3-NP at corresponding theoretical pressure of 6.130 MPa is 100％.The product purity is stabi-lized above 99％,showing that the product obtained by this process can be directly used without post-treatment.The product yield is high when the solid-to-liquid ratio(N-NP∶xylene)is 1∶3 in the hydrothermal method.Due to the low consumption,low cost,and low toxicity of rearrangement solvent,the hydrothermal method is expected to replace the traditional synthetic process of 3-NP.

为获得球形化高氯酸铵(AP),利用重力法测试了 AP在水中的溶解度,采用Vant't Hoff方程和Apelblat方程对溶解度数据进行拟合,建立溶解度模型;采用冷却结晶法制备了球形化AP晶体,分析了结晶液初始质量分数、搅拌速率、降温速率及养晶时间对产品形貌及粒度分布的影响;分别对非球形AP原料和球形化AP样品进行了吸湿性能、松散堆积密度、流散性、热稳定性的表征.结果表明,AP在水中的溶解度随着温度的升高而增加,Apelblat方程和Vant't Hoff方程的R2接近于1,且MAPD均小于3％;最佳冷却结晶工艺为:搅拌速率为230r/min,结晶液初始质量分数为35％,降温速率为0.5℃/min,养晶时间为3h;球形化AP样品的吸湿性能、松散堆积密度、流散性、热稳定性相比于非球形AP原料有明显改善.

为实时检测梯恩梯(TNT)生产过程中的凝固点温度,结合化学计量学和光谱学,采用偏最小二乘法建立近红外光谱分析技术,实时检测TNT凝固点温度的定量模型.通过比较1阶导数+标准正态变量变换(SNV)、多元散射校正(MSC)、1阶导数、SNV、1阶导数+MSC、2阶导数6种原始光谱数据优化预处理方法,发现选择光谱建模区间为9 403.8 ～4 597.7 cm-1、1阶导数(17点平滑)+ SNV预处理方法建立的模型最佳,模型相关系数R2=0.991,交互验证标准偏差为0.178.主成分分析及模型验证结果表明:用最优模型预测不同机台的硝化物凝固点温度,近红外光谱分析预测值与人工测定值偏差最大为0.950 4％;该模型有较好的稳定性、预测性,能够识别不同类型的样本,在短时间内用近红外光谱分析法可测定凝固点温度.

The solubilities of 3,4-dinitro-1H-pyrazole (DNP) in different solvents are essential for crystallization and further theoretical studies. In this paper, the solubilities of DNP in six pure solvents were determined in temperatures ranging from 298.15 K to 338.15 K by the dynamic laser monitoring method under atmospheric pressure. The results showed that the solubility of DNP in each tested solvent increases with the increasing temperature. Melting temperature T-m and fusion enthalpy Delta H-fus of DNP were determined using differential scanning calorimetry. Solubility data was correlated by the modified Apelblat equation, lambda h equation, Wilson model and nonrandom two-liquid (NRTL) model, and these results showed that all models can give satisfactory correlation results. Therefore, the experimental data and model parameters would provide essential support for industrial design. Furthermore, on the basis of the NRTL model and solubility data, the dissolution thermodynamic properties, including enthalpy, entropy, and Gibbs energy were determined.

The synthesis methods of p-nitro-n-methylamine(PNMA) were introduced. A synthesis process of PNMA from p-nitrochlorobenzen and methylamine under certain pressure was put forward. This process has many advantages, such as the convenient source of raw materials, low cost, less wastes and good product quality. This method is also suitable for industrial production. The structure of product was determined by elemental analysis, IR and MS.