發(fā)布時(shí)間：2018-07-16 15:23

【摘要】：烯烴氫氰化反應(yīng)是合成腈類化合物的重要反應(yīng),其中丁二烯氫氰化合成己二腈是烯烴氫氰化反應(yīng)中最重要的應(yīng)用。己二腈最重要的工業(yè)用途是作為生產(chǎn)尼龍66的原料。目前世界上己二腈的主要生產(chǎn)方法為丙烯腈電解二聚法和丁二烯直接氫氰化法且均被國(guó)外跨國(guó)公司所壟斷。其中丁二烯直接氫氰化法,具有工藝流程短、能耗低、無(wú)污染等優(yōu)點(diǎn)而受到廣泛關(guān)注。烯烴氫氰化反應(yīng)中催化劑的開發(fā)是其關(guān)鍵,因此研究探討新型催化劑催化3-戊烯腈氫氰化反應(yīng)制備己二腈對(duì)指導(dǎo)我國(guó)己二腈國(guó)產(chǎn)化具有重要意義。本文研究了3-戊烯腈氫氰化制備己二腈的催化體系,具體完成了以下工作:設(shè)計(jì)了一類新型氫蒽雙齒亞磷酸酯配體,并對(duì)其制備過(guò)程中的反應(yīng)條件進(jìn)行了篩選。通過(guò)考察投料方式、反應(yīng)溫度、溶劑以及堿等對(duì)反應(yīng)收率的影響,最終確定了較佳反應(yīng)條件:在-15℃下以甲苯為溶劑,三乙胺為有機(jī)堿,將酚滴加到三乙胺和三氯化磷的混合液中進(jìn)行反應(yīng),最終收率可達(dá)65.1%。采用該反應(yīng)條件分別制備了四種不同氫蒽雙齒亞磷酸酯配體,獲得了制備該類配體的通用方法。以氫蒽雙齒亞磷酸酯為配體,采用“原位”生成鎳催化劑的方法,考察了四種配體與鎳所組成的催化體系催化3-戊烯腈的氫氰化反應(yīng)。發(fā)現(xiàn)在相同的反應(yīng)條件下,配體L_(2c)(9,10-二氫蒽-四間甲苯基-1,8-雙亞磷酸酯)的催化效果最好。以L_(2c)配體,考察了其“原位”生成鎳催化劑催化3-戊烯腈氫氰化反應(yīng)的工藝條件。以丙酮氰醇為氰源,通過(guò)考察鎳源、還原劑、助催化劑、反應(yīng)溶劑、反應(yīng)溫度、反應(yīng)時(shí)間、鎳與丙酮氰醇的配比、配體與鎳的配比等因素對(duì)己二腈收率的影響,最終確定了3-戊烯腈氫氰化制備己二腈的較佳反應(yīng)條件:以四氫呋喃為反應(yīng)溶劑、氯化鎳為零價(jià)鎳來(lái)源、鋅粉為二價(jià)鎳的還原劑、氯化鋅為助催化劑、氯化鎳/丙酮氰醇(摩爾比)=1:10、配體/氯化鎳(摩爾比)=8:1、100℃下反應(yīng)4小時(shí),己二腈收率可達(dá)72.3%。以新型氫蒽雙齒亞磷酸酯為配體的催化體系的催化效果與文獻(xiàn)報(bào)道的雙齒類配體相當(dāng),但其具有制備過(guò)程簡(jiǎn)單、成本低、催化劑穩(wěn)定等優(yōu)點(diǎn),對(duì)進(jìn)一步探索新型氫蒽類雙齒亞磷酸酯鎳催化劑及其應(yīng)用具有重要意義。
[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，

本文編號(hào)：2126806