键合苯甲酸衍生物聚苯乙烯配体的合成及其Eu(Ⅲ)配合物的光致发光性能

Synthesis of Benzoic Acid Derivative-Bonded Polystyrene Ligand and Photoluminescence Properties of Its Complex with Eu(Ⅲ) Ion

使3-硝基-4-羟基苯甲酸(NHBA)的羟基与氯甲基化聚苯乙烯(CMPS)的氯甲基进行亲核取代反应,在聚苯乙烯侧链上引入硝基苯甲酸(NBA),制得了功能化的聚苯乙烯PS-NBA,考察了亲核取代反应的优化反应条件。并使之与Eu(Ⅲ)配位,制得了高分子-稀土配合物PS-(NBA)3-Eu(Ⅲ)。采用红外光谱(FTIR)和核磁共振氢谱(1H NMR)对PS-NBA的结构进行了表征,测试了配合物的荧光发射特性。结果表明,NHBA苯环上的硝基可降低CMPS与NHBA之间取代反应的速率,使用极性较强的溶剂N,N-二甲基甲酰胺及在较高的反应温度(70℃)下,有利于亲核取代反应的进行。大分子链上的配基NBA对Eu3+离子的荧光发射显示出很强的敏化作用,其敏化作用远强于苯甲酸(BA)配基,高分子-稀土配合物PS-(NBA)3-Eu(Ⅲ)具有比PS-(BA)3-Eu(Ⅲ)更强的荧光发射。

The nucleophilic substitution reaction between the chloromethyl group of chloromethylated polystyrene（CMPS） and phenolic hydroxyl group of 3-nitro-4-hydroxy benzoic acid（NHBA） was conducted, and the nitro-benzoic acid（NBA） ligand was bonded on the side chains of polystyrene（PS） to yield nitro-benzoic acid functionalization polystyrene PS-NBA. In this work, the nucleophilic substitution reaction between CMPS and NHBA was systematically investigated to optimize the reaction conditions. The coordination reaction between PS-NBA and Eu3＋ ion was carried out to give polymer-rare earth complex, PS-（NBA）3-Eu（Ⅲ）. The chemical structure of PS-NBA was characterized by FTIR and 1H NMR spectra and the florescence emission of PS-（NBA）3-Eu（Ⅲ） was preliminarily examined. The results show that the nitro substitute group in benzene ring can reduce the rate of the substitution reaction. The stronger polarity solvents and higher reaction temperature（70 ℃） favor the substitution reaction. The ligand NBA on the side chain of the functionalized polymer PS-NBA can strongly sensitize the fluorescence-emission of Eu3＋ ion, and its sensibilization is much stronger than that of benzoic acid（BA） ligand. The polymer-rare earth complex PS-（NBA）3-Eu（Ⅲ） possesses much stronger fluorescence emission intensity than PS-（BA）3-Eu（Ⅲ）.