酞菁类光电材料的合成研究
作者：刘宪锋
院校:天津大学
关键字:无金属酞菁,二氯酞菁硅,二羟基酞菁硅,合成
学位：硕士
专业:应用化学
摘要:
酞菁化合物是重要的光电材料，特别是硅酞菁化合物是新兴的载流子发生材料，它们的应用将越来越广泛，因此对它们的合成方法的研究和改进将有重大的现实意义。 本文建立了以酞菁素为原料，喹啉为溶剂，三甲氧基硅烷为供氢剂，合成无金属酞菁的新方法。并对反应时间、反应温度、原料配比等影响因素进行了研究，优化了工艺条件，得到的最佳反应条件是在酞菁素和三甲氧基硅烷的摩尔比为4:3，甲醇钠和三丁胺为添加剂，于220℃反应11h，无金属酞菁的最高收率为46.7％。 使用酞菁素和四氯化硅在喹啉中合成了二氯酞菁硅，初步探讨了反应的影响因素，得到的最佳反应条件是四氯化硅与1,3-二亚氨基异吲哚啉的摩尔比为3:2，在220℃反应0.5h，并采用甲醇析出法进行后处理，即将反应物冷却到80℃后倾入甲醇，打浆后趁热过滤得到产品，提高了分离生成物的成功率，产品收率为58.0％。 此外将合成的二氯酞菁硅采用两种方法转化为二羟基酞菁硅，第一种方法是碱处理法即将二氯酞菁硅在甲醇钠的乙醇溶液中回流得到，最高收率为53％第二种方法是酸处理法即采用二氯酞菁硅的硫酸溶液在冰水析出的方法转化为二羟基酞菁硅，其中酸溶析出法收率为77.0％。 采用红外、X-射线衍射、元素分析、差热分析等手段确认了上述化合物的结构、晶型、热稳定性等性能。
Abstract:
Phthalocyanine compound is a kind of important organic photoconductive material, especially silicon phthalocyanine is new CGL, so it is significant to studied and improve the synthetic method of the phthalocyanine. A new synthesis method of metal-free phthalocyanine using 1,3-diiminoiso- indoline as main material and trimethoxysilane as hydrogen donator was developed in this paper. The influences of reaction conditions such as material ratio, reaction temperature and time were studied.The optimum preparing condition was that the mole ratio of 1,3-diiminoiso- indoline and trimethoxysilane was 4:3,sodium methylate and tributylamine as additive ,reaction time 11h at 220℃, the yield of metal-free phthalocyanine was 46.7％. Silicon phthalocyanine dichloride was synthesized through the reaction of 1,3-diiminoisoindoline with silicon tetrachloride in quinoline. The reaction conditions was briefly studied, The optimum preparing condition was that the mole ratio of silicon tetrachloride and 1,3-diiminoiso- indoline was 3:2 , reaction time 0.5h at 220℃. The precipitation in methanol was carried out when the mixture was cooled to 80℃ and then to filtrate in order to separate the product successfully. The highest product yield was 58.0％. Silicon phthalocyanine dihydroxide was prepared from silicon phthalocyanine dichloride through two methods. The first was alkali treating that meaned silicon phthalocyanine dihydroxide was treated in the ethanol solution containing sodium methylate .The second was acid treating meaned precipitating its solution in concentrated sulfuric acid into ice water. The product yield of the second method was 77.0％, which was higher than the method of alkali treating. IR, X-ray diffraction analysis, elemental analysis and differential thermal analysis were used to determine the structure, crystalline form and thermal stability of compounds synthesized in this paper.