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.
出处
《化学研究与应用》
CAS
CSCD
北大核心
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)
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
Polysulfone
polymer-rare earth complex
p-Hydroxy benzaldehyde
3-aminopyridine
bidentate schiff base ligand
sensi-tization