氢蒽双齿镍催化剂催化3-戊烯腈氢氰化反应研究
发布时间：2018-07-16 15:23
【摘要】：烯烃氢氰化反应是合成腈类化合物的重要反应,其中丁二烯氢氰化合成己二腈是烯烃氢氰化反应中最重要的应用。己二腈最重要的工业用途是作为生产尼龙66的原料。目前世界上己二腈的主要生产方法为丙烯腈电解二聚法和丁二烯直接氢氰化法且均被国外跨国公司所垄断。其中丁二烯直接氢氰化法,具有工艺流程短、能耗低、无污染等优点而受到广泛关注。烯烃氢氰化反应中催化剂的开发是其关键,因此研究探讨新型催化剂催化3-戊烯腈氢氰化反应制备己二腈对指导我国己二腈国产化具有重要意义。本文研究了3-戊烯腈氢氰化制备己二腈的催化体系,具体完成了以下工作:设计了一类新型氢蒽双齿亚磷酸酯配体,并对其制备过程中的反应条件进行了筛选。通过考察投料方式、反应温度、溶剂以及碱等对反应收率的影响,最终确定了较佳反应条件:在-15℃下以甲苯为溶剂,三乙胺为有机碱,将酚滴加到三乙胺和三氯化磷的混合液中进行反应,最终收率可达65.1%。采用该反应条件分别制备了四种不同氢蒽双齿亚磷酸酯配体,获得了制备该类配体的通用方法。以氢蒽双齿亚磷酸酯为配体,采用“原位”生成镍催化剂的方法,考察了四种配体与镍所组成的催化体系催化3-戊烯腈的氢氰化反应。发现在相同的反应条件下,配体L_(2c)(9,10-二氢蒽-四间甲苯基-1,8-双亚磷酸酯)的催化效果最好。以L_(2c)配体,考察了其“原位”生成镍催化剂催化3-戊烯腈氢氰化反应的工艺条件。以丙酮氰醇为氰源,通过考察镍源、还原剂、助催化剂、反应溶剂、反应温度、反应时间、镍与丙酮氰醇的配比、配体与镍的配比等因素对己二腈收率的影响,最终确定了3-戊烯腈氢氰化制备己二腈的较佳反应条件:以四氢呋喃为反应溶剂、氯化镍为零价镍来源、锌粉为二价镍的还原剂、氯化锌为助催化剂、氯化镍/丙酮氰醇(摩尔比)=1:10、配体/氯化镍(摩尔比)=8:1、100℃下反应4小时,己二腈收率可达72.3%。以新型氢蒽双齿亚磷酸酯为配体的催化体系的催化效果与文献报道的双齿类配体相当,但其具有制备过程简单、成本低、催化剂稳定等优点,对进一步探索新型氢蒽类双齿亚磷酸酯镍催化剂及其应用具有重要意义。
[Abstract]:The hydrocyanidation of olefins is an important reaction in the synthesis of nitrile compounds, and the synthesis of adipic acrylonitrile from butadiene hydrocyanide is the most important application in the hydrocyanidation of olefins. The most important industrial use of adiponitrile is as a raw material for the production of nylon 66. At present, acrylonitrile electrolytic dimerization and butadiene direct hydrocyanidation are the main production methods in the world and are monopolized by foreign multinational corporations. Among them, butadiene direct hydrocyanic process has many advantages, such as short process flow, low energy consumption and no pollution. The development of catalyst is the key in hydrocyanidation of olefin, so it is very important to study the preparation of hexanitrile from 3-pentenitrile hydrocyanic reaction with new catalyst in order to guide the localization of hexanitrile in China. In this paper, the catalytic system of 3-pentene nitrile hydrogenation to prepare adipic acrylonitrile has been studied. The following work has been done: a new type of hydroanthracene didentate phosphite ligands were designed and the reaction conditions during the preparation were screened. The optimum reaction conditions were determined as follows: toluene as solvent, triethylamine as organic base, toluene as solvent and triethylamine as organic base at -15 鈩，
本文编号：2126806
[Abstract]:The hydrocyanidation of olefins is an important reaction in the synthesis of nitrile compounds, and the synthesis of adipic acrylonitrile from butadiene hydrocyanide is the most important application in the hydrocyanidation of olefins. The most important industrial use of adiponitrile is as a raw material for the production of nylon 66. At present, acrylonitrile electrolytic dimerization and butadiene direct hydrocyanidation are the main production methods in the world and are monopolized by foreign multinational corporations. Among them, butadiene direct hydrocyanic process has many advantages, such as short process flow, low energy consumption and no pollution. The development of catalyst is the key in hydrocyanidation of olefin, so it is very important to study the preparation of hexanitrile from 3-pentenitrile hydrocyanic reaction with new catalyst in order to guide the localization of hexanitrile in China. In this paper, the catalytic system of 3-pentene nitrile hydrogenation to prepare adipic acrylonitrile has been studied. The following work has been done: a new type of hydroanthracene didentate phosphite ligands were designed and the reaction conditions during the preparation were screened. The optimum reaction conditions were determined as follows: toluene as solvent, triethylamine as organic base, toluene as solvent and triethylamine as organic base at -15 鈩，
本文编号：2126806
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