侧链键合双齿席夫碱配基的聚苯乙烯的制备与表征及其Eu(Ⅲ)配合物荧光发射性能之初探  

Preparation and Characterization of Polystyrene Containing Bidentate Schiff Base Ligand on Side Chain and Preliminary Exploration of Fluorescence Emission Property of Its Eu(Ⅲ) Complexes

作　　者：徐迪[1] 高保娇[1] 陈萍虹 

机构地区：[1]中北大学化学工程系,太原030051

出　　处：《应用化学》2015年第2期183-191,共9页Chinese Journal of Applied Chemistry

基　　金：山西省自然科学基金资助项目(201002100843)~~

摘　　要：以1,4-二氯甲氧基丁烷为氯甲基化试剂,制备了氯甲基化聚苯乙烯(CMPS),使CMPS的氯甲基与对羟基苯甲醛(HBA)发生亲核取代反应,将苯甲醛(BA)键合在聚苯乙烯侧链,制得改性聚苯乙烯PS-BA;使PS-BA的醛基与3-氨基吡啶(AP)的伯氨基发生席夫碱反应,在聚苯乙烯侧链合成与键合了双齿席夫碱(SB)配基,制得了侧链键合有双齿席夫碱配基的功能化聚苯乙烯PS-SB。采用红外光谱(FTIR)和核磁共振氢谱(1H NMR)对其结构进行了表征。以大分子PS-SB为第一配体,以邻菲罗啉(Phen)为第二配体,与Eu(Ⅲ)离子配位,分别制得了二元和三元高分子-稀土配合物PS-(SB)3-Eu(Ⅲ)和PS-(SB)3-Eu(Ⅲ)-(Phen),初步探索了配合物的荧光发射性能。实验结果表明,对于CMPS与HBA之间的亲核取代反应,使用极性较强的N,N-二甲基乙酰胺为溶剂比较适宜,80℃为适宜的反应温度。大分子配体PS-SB对Eu(Ⅲ)离子的荧光发射可产生明显的敏化作用,二元和三元高分子-稀土配合物均发射出较强的Eu(Ⅲ)离子的特征荧光。Chloromethylated Polystyrene（CMPS） was first prepared with 1,4-bis（chloromethoxy） butane（BCMB） as the chloromethylation reagent. Then nucleophilic substitution between CMPS and phydroxybenzaldehyde（HBA） was conducted,resulting in benzaldehyde（BA） modified polystyrene（PS-BA）on its side chain. Finally,a reaction between 3-aminopyridine（AP） and the aldehyde group of PS-BA was allowed to form Schiff base functionalized polystyrene PS-SB. The chemical structure of PS-SB was characterized by FTIR and1 H NMR spectra. PS-SB as the first ligand and phenanthroline（Phen） as the second ligand,binary and ternary polymer-rare earth complexes,PS-（SB）3-Eu（Ⅲ） and PS-（SB）3-Eu（Ⅲ）-（Phen）,were prepared,respectively. The florescence emission properties of the two complexes were preliminarily explored. The experimental results show that the rate of the nucleophilic substitution reaction between CMPS and HBA has a mechanism of SN1. For the nucleophilic substitution reaction, N,Ndimethylacetamide（DMAC） with stronger polarity is a suitable solvent,and the temperature of 80 ℃ is appropriate. The macromolecular ligand PS-SB can produce obvious sensitization for the fluorescence emission of Eu（Ⅲ） ion,and both the binary and ternary complexes emit stronger characteristic fluorescence of Eu（Ⅲ）ion.

关 键 词：聚苯乙烯 高分子-稀土配合物 对羟基苯甲醛 氨基吡啶 双齿席夫碱配基 敏化作用 

分 类 号：O631[理学—高分子化学]