侧链键合双齿席夫碱配基聚砜的制备及大分子-Eu(Ⅲ)配合物荧光发射特性  

Preparation and characterization of functionalized polysulfone containing bidentate schiff base ligand on side chain and preliminary exploration of luminescence property of polymer-Eu(Ⅲ) complexes

作　　者：陈萍虹 高保娇[1] 徐迪[1] 

机构地区：[1]中北大学化学工程系,山西太原030051

出　　处：《化学研究与应用》2014年第12期1904-1911,共8页Chemical Research and Application

基　　金：山西省青年科学基金资助项目(2013021012-3)

摘　　要：在制备氯甲基化聚砜(CMPSF)的基础上,以对羟基苯甲醛(HBA)为试剂,通过亲核取代反应,将苯甲醛(BA)键合在聚砜侧链,制得改性聚砜PSF-BA;接着,又使3-氨基吡啶(AP)与PSF-BA的醛基发生席夫碱反应,在聚砜侧链合成与键合了双齿席夫碱(SB)配基,形成了侧链键合有双齿席夫碱配基的功能化聚砜PSFSB。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PSF-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PSF-(SB)3-Eu(Ⅲ)和PSF-(SB)3-Eu(Ⅲ)-(Phen)1,初步探索了配合物的荧光发射性能。本文重点研究了功能化聚砜PSF-SB的制备反应及表征,考察了主要因素对CMPSF与HBA之间亲核取代反应的影响规律,分析了反应机理,优化了反应条件。实验结果表明,对于CMPSF与HBA之间的亲核取代反应,极性较强的N,N-二甲基乙酰胺为适宜的溶剂,90℃为适宜的反应温度。大分子配体PSF-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-稀土配合物都发射出较强的Eu(Ⅲ)离子特征荧光。On the basis of preparing chloromethylatedpolysulfone（ CMPSF） ,benzaldehyde（ BA） was bonded on the side chain of PSF via nucleophilic substitution with p-hydroxy benzaldehyde as the reagent, resulting in the modified polysulfone PSF-BA. Subsequently,a Schiff base reaction between 3-aminopyridine and the aldehyde group of PSF-BA was allowed to be carried out, and Schiff base ligands were bonded on the side chain of PSF,forming functionalized polysulfone PSF-SB containing bidentate Schiff base ligand on side chain. The chemical structure of PSF-SB was characterized by FTIR and 1 H-NMR spectra. The coordination re-action between PSF-SB as well as phenanthroline（ Phen） and Eu3＋ion was allowed to be conducted,and the binary and ternary poly-mer-rare earth complexes,PSF-（ SB） 3-Eu（Ⅲ） and PSF-（ SB） 3-Eu（Ⅲ）-（ Phen） 1 were prepared. The fluorescence emission proper-ties of the two complexes were preliminarily explored. In this work,the preparation reaction of the functionalized polysulfone PSF-SB was mainly investigated. The effects of the main factors on the nucleophilic substitution reaction between CMPSF and HBA were ex-amined,the reaction mechanism was investigated,and the reaction conditions were optimized. The experimental results show that the rate of the nucleophilic substitution reaction has a mechanism of SN1. N,N-dimethylacetamide with stronger polarity is a suitable solvent,and the appropriate reaction temperature is 90℃. The macromolecular ligand PSF-SB can produce obvious sensitization ac-tion for the fluorescence emission of Eu（Ⅲ） ion,and both the binary and ternary complex emit stronger characteristic floredcence than Eu（Ⅲ） ion.

关 键 词：高分子-稀土配合物 对羟基苯甲醛 3-氨基吡啶 双齿席夫碱配基 敏化作用 

分 类 号：O633.4[理学—高分子化学]