芳羧酸功能化聚砜的制备及其与Tb（Ⅲ）离子配合物荧光发射特性的初探

摘要

以对氯甲基苯甲酸（CMBA）为试剂,通过Friedel-Crafts烷基化反应,将苯甲酸（BA）键合在聚砜（PSF）侧链,制得了改性聚砜BAPSF,并采用FT IR与1H NMR等方法对其结构进行了表征。通过与Tb3＋配位,制得了高分子-稀土配合物BAPSF-Tb（Ⅲ）,初步考察了该配合物的荧光发射特性。本文重点研究了聚砜的功能化改性反应,考察了主要因素对CMBA与PSF之间Friedel-Crafts烷基化反应的影响,分析了反应机理,优化了反应条件。实验结果表明,CMBA与PSF之间Friedel-Crafts烷基化反应顺利进行的适宜反应条件为：70℃,以N,N-二甲基乙酰胺（DMAC）为溶剂,SnCl4为催化剂。配合物BAPSF-Tb（Ⅲ）不仅发射出Tb3＋的特征荧光,而且大分子配基BAPSF对Tb3＋的荧光发射显示出很强的敏化作用。%Polysulfone（PSF） was functionalization-modified with 4-chloromethyl benzoic acid（CMBA） as reagent via Friedel-Crafts alkylation to obtain the functional macromolecule BAPSF in which benzoic acid（BA） ligand was bonded on the side chains of PSF.The chemical structure of BAPSF was characterized by FT IR and 1H NMR.The polymer-rare earth complex,BAPSF-Tb（Ⅲ） was prepared by the coordination between BAPSF and Tb3＋.The florescence emission of BAPSF-Tb（Ⅲ） was preliminarily explored.In this work,the main effect factors on the Friedel-Crafts alkylation between CMBA and PSF were investigated and the reaction mechanism was discussed.The results showed that the optimal conditions of the Friedel-Crafts alkylation between CMBA and PSF are as follows： at temperature of 70℃,with N,N-dimethylacetylamide（DMAC） as solvent,and SnCl4 as Lewis catalyst.The complex BAPSF-Tb（Ⅲ） not only emitted the fluorescence of Tb3＋,but also the intensity could be strongly sensitized by macromolecular ligand BAPSF.