芳羧酸功能化聚苯乙烯的制备及其与Tb(Ⅲ)离子配合物荧光发射特性初探

Preparation of Aryl Carboxylic Acid-functionalized Polystyrene and Preliminary Exploration of Florescence Emission of Formed Polymer-Rare Earth(Tb(Ⅲ)) Complexes

通过氯甲基苯甲酸(CMBA)的Friedel-Crafts烷基化反应,对聚苯乙烯(PS)进行了功能化改性,将苯甲酸(BA)键合在聚苯乙烯侧链,制得了改性聚苯乙烯(BAPS),采用红外光谱、核磁共振氢谱及紫外吸收光谱等测试技术对其进行了结构表征,考察了影响CMBA与PS之间Friedel-Crafts烷基化反应的主要因素。结果表明,适宜的反应条件为:70℃,以N,N-二甲基乙酰胺为溶剂,SnCl4为催化剂。使BAPS与Tb(Ⅲ)离子配位,制得高分子-稀土配合物BAPS-Tb(Ⅲ),该配合物不仅发射出Tb3+离子的特征荧光,而且大分子配基BAPS对Tb3+离子的荧光发射显示出很强的敏化作用。

Polystyrene （PS） was modified with 4-（chloromethyl） benzoic acid （CMBA） via Friedel-Crafts alkylation reaction, where benzoic acid （BA） ligand was bonded on the side chains of PS, yielding the functional macromolecule BAPS., The chemical structure of BAPS was characterized by FTIR, 1H NMR and UV absorption spectra. The coordination reaction between BAPS and Eu3＋ ion as well as the coordination reaction between BAPS and Tb3＋ iop were carried out, resulting in the polymer/rare-earth complexes, BAPS- Tb （ Ⅲ）. The florescence emission of BAPS-Tb （Ⅲ） was preliminarily examined. In this work, the effects of the main factors on the Friedel-Crafts alkylation action between CMBA and PS were examined, the reaction mechanism was investigated, and the reaction conditions were optimized. The experimental results show that the Friedel-Crafts alkylation reaction between CMBA and PS can proceed successfully, and the suitable reaction conditions are as follows： a temperature of 70 ℃, with N, N-dimethylaeetylamide （DMAC） as solvent, and SnC14 as Lewis catalyst. The polymer/rare-earth complex BAPS-Tb （IU）, possesses the fluorescence-emission spectrum of Tb3＋ ion. More significantly, the macromolecular ligand BAPS can strongly sensitize the fluorescence-emission of Tb3＋ ion.