【作者】 翟林峰；

【导师】 史铁钧；

【作者基本信息】 合肥工业大学 ， 应用化学， 2003， 硕士

【摘要】 N-乙烯基吡咯烷酮（N-vinylpyrrolidone）简称NVP，是一种有机合成原料，主要用于合成聚乙烯吡咯烷酮（Polyvinylpyrrolidone）简称PVP。PVP是一种水溶性的高分子，具有优异的溶解性、成膜性和保护胶作用，被广泛用于医药、化妆品和食品等部门。迄今为止，NVP的合成方法主要包括乙炔法和非乙炔法。世界上生产NVP的方法主要是Reppe法，该法以乙炔为原料，在高温高压条件下合成NVP。不仅条件苛刻，投资大，能耗大，而且存在乙炔爆炸的危险，只适合于大规模生产。非乙炔法有γ-丁内酯法、醇交换法、醚交换法等。本课题主要研究最具有工业前景的γ-丁内酯法。γ-丁内酯法即以γ-丁内酯为原料通过与乙醇胺反应得到氨解产物N-羟乙基吡咯烷酮（N-hydroxyethy-2-pyrrolidone）简称NHP，然后对该氨解产物进行间接或直接脱水得到目标产物NVP，该工艺具有反应步骤少、操作条件温和等特点。本课题首先以HY分子筛等为催化剂，对氨解工艺进行研究并对其做了改进；然后分别采用间接法和直接法对氨解产物NHP进行脱水得到NVP，其中间接脱水法采用浓盐酸做氯代剂，再用氢氧化钠醇溶液对其进行脱氯化氢反应得到NVP：直接法脱水是采用了HY分子筛等催化剂对NHP进行气相反应直接脱水得到NVP；并利用IR、GC、XRD、DSC等仪器对反应的中间体和产物进行表征同时对各步反应的机理做了探讨。实验结果表明，γ-丁内酯法合成NVP的最佳工艺条件为：（1）NHP的合成：常压下，以HY分子筛为催化剂，反应温度185℃，反应时间12h，原料配比n（γ-丁内酯）：n（乙醇胺）=1：1。所得NHP的收率为88.2％，其选择性为96.5％。（2）NHP间接脱水法：a、氯代过程：常压下，以浓盐酸为卤代剂，AlCl₃为催化剂，加热温度150℃，反应时间4h，原料配比n（NHP）：n（HCl）=1：1.2，所得NHP的收率为87.5％，其选择性为95.3％。b、乙烯化过程：以异丙醇为溶剂，反应温度65℃，反应时间3h，原料配比n（NClP）：n（NaOH）=1：1.2，溶剂量V（NClP）：V（异丙醇）=1：1.5，反应产物的收率为85.0％，其选择性为90.7％。（3）NHP直接脱水法：在较低的滴加速度6mL／min和较大真空度0.092Mpa下，以HY型分子筛为催化剂，催化剂的颗粒大小为80～100目，反应温度350士10℃，所得的NVP收率为41 .2%，选择性为75.2%。更多还原

【Abstract】 N-vinylpyrrolidone(NVP) is an organic synthetic raw material which is mainly applied in preparation of Poly-vinlypyrrolidone(PVP). PVP is a water soluble high molecular weight polymer. It has solubility, membranous form property and protective -glue actions. PVP is widely used as medicine binding agents, cosmetic additives and foodstuff additives.So far, the ways of synthesizing NVP manly include acetylene method and nonacetylene method. A world widely used method of producing NVP is Peppe method in which raw meterial acetylene is treated at high temperature and high pressure. Not only is the reaction condition harsh, the equipments in investment and the energy consumption large, but also exists the danger of acetylene explosion, so the Reppe method suits large-scale production only.The nonacetylene method includes the method of y -butyrolactone, mellow exchange, aether exchange and so on. This subject is mainly about the most prospective Y -butyrolactone method, in which first N-hydroxyethyl-2-pyrrolidone (NHP) is prepared by ammonolysis of r-butyrolactone and ethanol amine, then NVP is gained by direct or indirect dehydration of NHP. This technology has virtues of fower reaction steps and mild operation condition.In this study, first the technology of ammonolysis is studied and improved by using HY molecular sieves as catalyst, and then NVP is gained by direct or indirect dehydration of ammonolysis product NHP. In the indirect dehydration, hydrochloric acid first reacts with NHP, and then sodium hydroxide and its alcohol solution are used to get NVP; In the direct method, NHP is dehydrated directly in gas-phase on HY molecular sieves to get NVP; at the same time, IR, GC, XRD, DSC are adopted to token the reactive intermediates and products and the reactive mechanisms are studied.From the results, the best technology conditions is as follows:(1) The synthesis of NHP: general pressure, HY molecular sieves as catalyst, reaction temperature 185℃, reaction time 12h, molar ratio of Y -butyrolactone and ethanolamine 1:1. The yield of NHP is 88.2% and the selectivity is 96.5%.(2) The indirect dehydration of NHP: a Halide : general pressure, hydrochloric acid as halide, ACl3 as catalyst, heater temperature 150℃, reaction time 4h, molar ratio of NHP and HC1 1:1.2, the yield of NC1P is 87.5%, and the selectivity is 95.3%. b ethylenation: isopropanol as solvent, reaction temperature 65℃, reaction time 3h,molar ratio of NC1P and NaOH 1:1.2, the quantity of solvent NC1P and isopropanol 1:1.5, the yield of NVP is 85.0% and its selectivity is 90.7.(3) The direct method of NHP: At a lower drop rate 6mL/min and a higher vacuum degree 0.092Mpa, HY molecular sieves as catalyst, the size of the catalyst is 80~100mu,reaction temperature 350℃ ±+ 10℃, the yield of NVP is 41.2% and the selectivity is 75.2%.更多还原