【作者】 杨云峰；

【导师】 高保娇；

【作者基本信息】 华北工学院 ， 军事化学与烟火技术， 2004， 硕士

【摘要】 本研究首先以聚丙烯酸（PAA）与氯化亚砜作用，生成聚丙烯酰氯，然后与8-羟基喹啉（8HOQ）反应，制备了带有8-羟基喹啉侧基的聚丙烯酸（PAA8q），实现了8-羟基喹啉高分子化；通过PAA8q与稀土元素Eu（Ⅲ）的配位反应，得到了稀土Eu（Ⅲ）－高分子化8-羟基喹啉配合物（Eu-PAA8q），并确定了制备配合物的最佳条件。通过紫外光谱、红外光谱研究了PAA8q的分子组成与结构，以容量法确定了稀土高分子化8-羟基喹啉配合物中Eu（Ⅲ）的含量及配合物的结构，通过荧光光谱法详细研究了稀土配合物的荧光特性及其发光机理。研究结果表明，聚丙烯酰氯与8-羟基喹啉作用，首先发生酯化反应，然后经弗里斯重排反应实现喹啉环上酰基化反应，使8-羟基喹啉高分子化，得率为36.5％，平均每15.6个聚丙烯酸结构单元含有一个8-羟基喹啉分子；8-羟基喹啉的配位能力强，当PAA8q与三氯化铕作用生成配合物时，首先以8-羟基喹啉配位为主，反应最佳条件为PAA8q中8-羟基喹啉的含量与三氯化铕的配比为1:1，pH=7.5，反应温度为45℃，时间为45min；稀土Eu（Ⅲ）－高分子化8-羟基喹啉配合物中，8-羟基喹啉具有较大的共轭体系，容易发生π-π*跃迁而吸收能量，稀土离子Eu（Ⅲ）f*能级与8-羟基喹啉的最低三重态能级相匹配，从而发生从配体8-羟基喹啉的最低三重态能级到稀土Eu（III）离子f* 能级的分子内能量传递，8HOQ具有强的“天线效应”，使配合物的荧光强度较三氯化铕增强了近14倍。更多还原

【Abstract】 In this investigation, polyacryloyl chloride was prepared by reacting of polyacrylic acid ( PAA) with SOCl2 firstly, then it was used to react with 8-hydroxylquinoline (8HOQ), the PAA containig 8HOQ side groups was synthesized, which is designated as PAA8q, so the incorporating of 8-hydroxylquinoline into macromolecules was realized. The complex of Eu(Ⅲ)- PAA8q was obtained by coordination reaction of PAA8q with rare-earth ion Eu(Ⅲ), the rare-earth—polymer complex the structure and composition of the rare-earth—polymer complex was characterized using FTIR and UV, its content of Eu(Ⅲ) was measured by volumetric method, and its fluorescence character and emission mechanism was studied on details. The results show that the esterifying reaction occurs firstly, in turn the Friess rearrangement reaction takes place and quinoline ring is acylated when polyacryloyl chloride interreacts with 8HOQ, so that the incorporating 8HOQ into macromolecules is realized. The yield of 8HOQ incorporating into macromolecules is 36.5%, and there is one 8-hydroxylquinoline molecule in 15.6 units of PAA on an average. Owing to the stronger coordinating ability of 8-hydroxylquinoline as ligand，the coordination reaction of 8HOQ with Eu(Ⅲ)is predominant over the coordination reaction of -COOH in PAA8q. The optimum reaction conditions for the coordination reaction determined are as follows. The feed ratio of 8HOQ in PAA8q to EuCl3 is 1:1, pH is 7.5, the reaction temperature is 45℃, and the reaction time is 45 min. The complex of Eu(Ⅲ)- PAA8q has stronger ability of absorbing energy because of great conjugate system of 8-hydroxylquinoline molecule and easieness of π-π* transition. Besides, the f* energy level of ion Eu(Ⅲ) is matchable with the lowest energy level of triplet state of 8-hydroxylquinoline, and the intramolecular energy transfer occurs from 8-hydroxylquinoline to Eu(Ⅲ) easily, i.e. 8-hydroxylquinoline is called to have ‘aerial effect’, so that The complex of Eu(Ⅲ)- PAA8q has stronger fluorescence emission, and its intensity of fluorescence emission is 14 times stronger than EuCl3.更多还原