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

doi:10.3724/SP.J.1095.2014.30186

摘要/Abstract

摘要： 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。

关键词: 聚苯乙烯, 硝基苯甲酸配基, 亲核取代反应, 高分子-稀土配合物, 荧光发射, 敏化作用

Abstract: 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).

Key words: polystyrene, nitro-benzoic acid ligand, nucleophilic substitution, polymer-rare earth complex, fluorescence- emission, sensibilization

中图分类号:

O631

许泽清, 高保娇, 侯晓东. 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[J]. 应用化学, DOI: 10.3724/SP.J.1095.2014.30186.

XU Zeqing, GAO Baojiao*, HOU Xiaodong. Synthesis of Benzoic Acid Derivative-Bonded Polystyrene Ligand and Photoluminescence Properties of Its Complex with Eu(Ⅲ) Ion[J]. Chinese Journal of Applied Chemistry, DOI: 10.3724/SP.J.1095.2014.30186.

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