导　　师： 王乐夫;崔英德

学科专业： 081705

授予学位： 博士

作　　者： ;

机构地区： 华南理工大学

摘　　要： 聚乙烯吡咯烷酮/(PVP/)作为一种高分子精细化学品，具有优异的溶解性、生理相容性、成膜性、化学稳定性、粘接性以及络合或吸附某些小分子的能力等，因而在医药、医疗卫生、化妆品、食品饮料、纺织印染、新材料等领域具有重要的功能。PVP产生于20世纪30年代，由BASF公司化学家W．Reppe以乙炔为主要原料经乙炔的醛加成、催化加氢、催化脱氢、氨化、炔加成、聚合六步合成，称为乙炔法，迄今为止，乙炔法仍然是PVP及其单体的主要合成方法，但该法存在乙炔有潜在的爆炸危险性、反应需要在高压下进行、步骤多等难以克服的缺点，导致至今只有BASF和ISP两家公司采用该法，正在研究中的γ-丁内酯法及其他方法尚不成熟，所以开展PVP及其单体的合成方法与生产工艺的研究开发工作具有重要的意义。 本文以γ-丁内酯法为出发点，以γ-丁内酯与乙醇胺为原料，经过气相催化胺解反应与胺解产物NHP的催化脱水两步得到PVP单体，重点对γ-丁内酯与乙醇胺的反应进行了研究，主要的研究内容与结论如下： 1．用金属盐溶液浸渍的方法对Y型分子筛与NaZSM-5分子筛进行了改性，研究了这两种改性分子筛对γ-丁内酯与乙醇胺之间反应合成NHP的催化性能，结果表明，不同组成分子筛的活性各不相同，Y型分子筛的活性总体上高于ZSM-5型分子筛，而ZSM-5型分子筛的稳定性则较Y型分子筛好。Y型分子筛中，HY、Cu-NaY、REY、Cu-REY四种分子筛具有较高的活性，其中Cu-NaY具有最高的初始活性，而REY、Cu-REY具有比较理想的稳定性。以分子筛的组成和结构对实验结果进行了解释。在此基础上，以Cu-REY为催化剂，讨论了主要工艺条件对反应的影响，并确定了较佳的反应条件为：反应温度为260℃～280℃，接触时间25～30g·h·mol~/(-1/)，反应物摩尔比乙 Polyvinylpyrrolidone/(PVP/) plays an important role in many fields such as medicine, iatrosanitary, cosmetics, food-beverage, new materials as a fine polymer chemical because of its high properties of solubility, low toxicity, chemical stability, adhesivity and complexity with or adsorptivity of some micromoleculars. PVP was synthesized in 1930s by W.Reppe through Ethyne Method including addition of formaldehyde to ethyne, catalytic hydrogenation, catalytic dehydrogenation, amination, addition of formaldehyde to pyrrolidone and polymerization of NVP. Hitherto, major PVP products are still produced by this method in which ethyne is hazardous, high pressure and multisteps are needed. Other methods including y-butyrolactone method are in research stage. So it is of great significance to do research for synthesis method and production technology of PVP and its monomer. In this dissertation, N-vinylpyrrolidone, that is monomer for PVP, is synthesized through gas catalytic reaction of y-butyrolactone and ethanolamine and catalytic dehydration of hydroxyethenylpyrrolidone /(NHP/) . Works focus on the amination reaction. Main contents and conclusions are below: 1. Y zeolites and NaZSM-5 zeolite are modified by impregnating method using nitrate salts. Activities of the modified zeolites for the reaction of γ-butyrolactone and ethanolamine to give NHP are studied. It is found that the activities of zeolites change with their composition and Y zeolites show higher activities than ZSM-5 zeolites generally and ZSM-5 zeolites show higher stability. HY, Cu-NaY, REY and Cu-REY have comparatively high NHP yields. Original activity of Cu-NaY is the highest but decreases rapidly. Cu-REY has the highest stability. Influences of main conditions on the reaction are investigated and the conditions optimized are below: reaction temperature 260℃ ~ 280℃ , contact time 25~30g·h·mol~/(-1/), molar ratio of ethanolamine to y-butyrolactone 4~5, the ratio of reactants to N/_2 1～2, catalyst use level 5g and catalyst

关 键 词： 单体 丁内酯 催化合成 动力学 羟基吡咯烷酮

领　　域： [理学] [理学]