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酮连氮化合物具有共轭双键（-C＝N-N＝C-），化学活性强能够发生多类反应，广泛应用于医药中间体、感光材料、可聚合单体、染料、航空燃料等众多工业领域。本文针对环丙基甲基酮和水合肼的缩合反应，优化了反应条件，测定了反应焓变和动力学，表征了产物环丙基甲基酮连氮（C10N2H16）的结构，系统测定了其物化性质。主要进展如下： （1）环丙基甲基酮连氮的合成及反应优化。通过酮和水合肼反应合成了环丙基甲基酮连氮。经蒸馏、柱层析纯化后，对其结构进行一系列表征。测定了反应热，得到反应焓变和吉布斯自由能等。在常压下，分别研究反应转速、环丙基甲基酮与肼的摩尔比、温度、时间和溶剂对反应的影响。在优化的反应条件下（转速500 rpm、摩尔比2：1、温度363.2 K、时间7 h），经气相色谱测定，环丙基甲基酮连氮的产率达93.6%，环丙基甲基酮的转化率达96.80%。在此基础上，建立了宏观反应动力学模型，计算了反应级数和活化能等参数。（2）环丙基甲基酮连氮的物化性质测定和关联。在温度范围为（280 ~ 400 K）区间内，测定了环丙基甲基酮连氮的密度（ρ，0.884 ~ 0.947 g·cm-3）、动态粘度（η，1.39 ~2.88 mPa）、比热容（Cp，2.03 ~ 2.32 J·g-1·K-1）、表面张力（γ，22.1 ~25.0 mN·m-1）等。结果显示，ρ、η、γ与温度呈正相关，Vm、α、Cp与温度呈负相关。针对环丙基甲基酮+环丙基甲基酮连氮体系，实验测定了气液相平衡，并应用NRTL模型数值关联得到二元交互参数。综上所述，文中合成了新型的环丙基甲基酮连氮，测定了反应焓变与动力学，得到了环丙基甲基酮连氮的物化参数。以上工作为实现环丙基甲基酮连氮的工业化应用提供了重要的基础支撑。;Ketazines as a class of compounds with conjugated double bonds (-C＝N-N＝C-) show many special properties and high reactivities. Up to now, ketazines are extensively applied in many industrial fields, including pharmaceutical intermediates, photosensitive materials, polymerizable monomers, dyes, as well as aviation fuels. For the condensation reaction of cyclopropyl methyl ketone and hydrazine hydrate, we optimized the reaction conditions, measured the reaction enthalpy and kinetics, characterized the structure of cyclopropyl methyl ketazine as well as obtained a series of its physicochemical properties. The main contents are summarized as follows: (1) Cyclopropyl methyl ketazine was prepared from cyclopropyl methyl ketone and hydrazine hydrate. A series of characterizations were performed after the product was purified through distillation and column chromatography. The reaction heat was measured, as well as the enthalpy and Gibbs free energy were obtained. Under the atmospheric pressure, the reaction was studied at different rotation rate, mole ratios of cyclopropyl methyl ketone to hydrazine, reaction temperatures, and reaction times. With the optimized reaction conditions at 2:1, 363.2 K and 7 h, the yield of cyclopropyl methyl ketazine was up to 93.6% and the conversion rate of ketone was up to 96.8% through the chromatograph measurements. The reaction kinetic model was established, and parameters such as reaction order and activation energy were calculated. (2) Measurement and correlation of physicochemical parameters of cyclopropyl methyl ketazine in a temperature range (280 ~ 400 K). Parameters were acquired including density (ρ, 0.884 ~ 0.947 g·cm-3), dynamic viscosity (η, 1.39 ~2.88 mPa), heat capacity (Cp, 2.03 ~ 2.32 J·g-1·K-1), surface tension (22.1 ~25.0 mN·m-1), etc. The data of ρ, η and γ exhibit the positive correlations with temperature, while Vm, α, and Cp show the negative correlations, which all have a good fitting degree for equations. Considering the cyclopropyl methyl ketazine reaction systems, the vapor-liquid equilibria (VLE) of binary system (cyclopropyl methyl ketone + cyclopropyl methyl ketazine) were measured, and correlated with NRTL model to acquire the binary interaction parameters. In summary, a new ketazine (cyclopropyl methyl ketzaine) was prepared in this work. The reaction enthalpy and kinetics were measured, and a complete set of physicochemical parameters of cyclopropyl methyl ketazine were obtained. The above work provide an important foundation for the industrial application of cyclopropyl methyl ketazine.
|赵文昭. 酮/肼反应制备环丙基甲基酮连氮研究[D]. 中国科学院大学,2020.|
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