氨基酚型双齿席夫碱配基功能化聚砜的制备及其与Eu(Ⅲ)离子所形成的配合物的光致发光性能

Preparation of Aminophenol Type Bidentate Schiff Base LigandFunctionalized Polysulfone and Photoluminescence Property of Complexes Constituted by Macromolecular Ligand and Eu(Ⅲ)Ion

以对氯甲基苯甲醛(CMBA)为试剂,使聚砜(PSF)发生Friedel-Crafts烷基化反应,将苯甲醛(BA)键合在PSF侧链,制得改性聚砜PSF-BA,并考察了主要因素对Friedel-Crafts烷基化反应的影响规律;然后,使PSF-BA的醛基分别与邻氨基苯酚(OAP)及间氨基苯酚(MAP)的氨基发生缩合反应,从而在PSF侧链实现了氨基酚型双齿席夫碱配基的同步合成与键合,获得了2种功能化聚砜PSF-BAOA和PSF-BAMA。采用红外光谱(FT-IR)和核磁氢谱(1 H-NMR)对功能化聚砜的化学结构进行了表征。最后,使大分子配体PSF-BAOA和PSF-BAMA分别与Eu(Ⅲ)离子发生配位反应,制备了光致发光二元高分子-稀土配合物PSF-(BAOA)3-Eu(Ⅲ)与PSF-(BAMA)3-Eu(Ⅲ)。结果表明:溶剂的极性有利于聚砜与CMBA之间的Friedel-Crafts烷基化反应,适宜的溶剂为N,N-二甲基乙酰胺;适宜的温度为70℃。大分子配体PSF-BAOA和PSFBAMA对Eu(Ⅲ)离子的荧光发射均会产生强烈的敏化作用,2种二元高分子-稀土配合物均发射出强烈的Eu(Ⅲ)离子特征荧光。

The Friedel-Crafts alkylation reaction was carried out between polysulfone （PSF） and 4-（chloromethyl）benzaldehyde （CMBA）,and benzaldehyde （BA） as a group was bonded on the side chain of PSF,resulting in the modified polysulfone PSF-BA,and the effects of the main factors on the Friedel-Crafts alkylation reaction between PSF and CMBA were examined.Subsequently,the condensation reaction between the aldehyde group of PSF-BA and the amino group of ortho-aminophenol （OAP） or meta-aminophenol （MAP） was performed,and the synchronous synthesis and bonding of aminophenol type bidentate Schiff base ligand on the side chain of PSF were realized,obtaining two functional PSFs,PSF-BAOA and PSF-BAMA.The chemical structures of the functional PSFs were characterized by FT-IR and ^1H-NMR spectra.Finally,the two macromolecular ligands,PSF-BAOA and PSF-BAMA,were coordinated with Eu（Ⅲ） ion,respectively,and two binary photoluminescence polymer-rare earth complexes,PSF-（BAOA）3-Eu（Ⅲ） and PSF-（BAMA）3-Eu（Ⅲ） were prepared.Results showed that the polarity of the solvent was beneficial to the Friedel-Crafts alkylation reaction between PSF and CMBA,and N,N-dimethylacetamide was a suitable solvent,the appropriate temperature was 70℃.Both PSF-BAOA and PSF-BAMA could effectively sensitize the fluorescence emission of Eu（Ⅲ） ion,and the two binary polymer-rare earth complexes emitted strong characteristic fluorescence of Eu（Ⅲ） ion.