侧链键合双齿席夫碱配基的聚苯乙烯的制备与表征及其Eu(Ⅲ)配合物荧光发射性能之初探

doi:10.11944/j.issn.1000-0518.2015.02.140176

摘要/Abstract

摘要：

以1,4-二氯甲氧基丁烷为氯甲基化试剂,制备了氯甲基化聚苯乙烯(CMPS),使CMPS的氯甲基与对羟基苯甲醛(HBA)发生亲核取代反应,将苯甲醛(BA)键合在聚苯乙烯侧链,制得改性聚苯乙烯PS-BA;使PS-BA的醛基与3-氨基吡啶(AP)的伯氨基发生席夫碱反应,在聚苯乙烯侧链合成与键合了双齿席夫碱(SB)配基,制得了侧链键合有双齿席夫碱配基的功能化聚苯乙烯PS-SB。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PS-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PS-(SB)₃-Eu(Ⅲ)和PS-(SB)₃-Eu(Ⅲ)-(Phen),初步探索了配合物的荧光发射性能。实验结果表明,对于CMPS与HBA之间的亲核取代反应,使用极性较强的N,N-二甲基乙酰胺为溶剂比较适宜,80 ℃为适宜的反应温度。大分子配体PS-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-稀土配合物均发射出较强的Eu(Ⅲ)离子的特征荧光。

关键词: 聚苯乙烯, 高分子-稀土配合物, 对羟基苯甲醛, 氨基吡啶, 双齿席夫碱配基, 敏化作用

Abstract:

Chloromethylated Polystyrene(CMPS) was first prepared with 1,4-bis(chloromethoxy) butane(BCMB) as the chloromethylation reagent. Then nucleophilic substitution between CMPS and p-hydroxybenzaldehyde(HBA) was conducted, resulting in benzaldehyde(BA) modified polystyrene(PS-BA) on its side chain. Finally, a reaction between 3-aminopyridine(AP) and the aldehyde group of PS-BA was allowed to form Schiff base functionalized polystyrene PS-SB. The chemical structure of PS-SB was characterized by FTIR and ¹H NMR spectra. PS-SB as the first ligand and phenanthroline(Phen) as the second ligand, binary and ternary polymer-rare earth complexes, PS-(SB)₃-Eu(Ⅲ) and PS-(SB)₃-Eu(Ⅲ)-(Phen), were prepared, respectively. The florescence emission properties of the two complexes were preliminarily explored. The experimental results show that the rate of the nucleophilic substitution reaction between CMPS and HBA has a mechanism of S_N1. For the nucleophilic substitution reaction, N,N-dimethylacetamide(DMAC) with stronger polarity is a suitable solvent, and the temperature of 80 ℃ is appropriate. The macromolecular ligand PS-SB can produce obvious sensitization for the fluorescence emission of Eu(Ⅲ) ion, and both the binary and ternary complexes emit stronger characteristic fluorescence of Eu(Ⅲ) ion.

Key words: polystyrene, polymer-rare earth complex, p-hydroxybenzaldehyde, aminopyridine, bidentate, Schiff base ligand, sensitization

中图分类号:

O631

徐迪, 高保娇, 陈萍虹. 侧链键合双齿席夫碱配基的聚苯乙烯的制备与表征及其Eu(Ⅲ)配合物荧光发射性能之初探[J]. 应用化学, 2015, 32(2): 183-191.

XU Di,GAO Baojiao ,CHEN Pinghong. Preparation and Characterization of Polystyrene Containing Bidentate Schiff Base Ligand on Side Chain and Preliminary Exploration of Fluorescence Emission Property of Its Eu(Ⅲ) Complexes[J]. Chinese Journal of Applied Chemistry, 2015, 32(2): 183-191.

参考文献

[1] Hilder M,Junk P C,Kynast U H, et al . Spectroscopic Properties of Lanthanoid Benzene Carboxylates in the Solid State:Part 1[J]. J Photochem Photobiol A : Chem ,2009,202(1):10-20.
[2] Xi P,Gu X H,Chen C F, et al . Synthesis, Characterization and Luminescent Properties of New Highly Luminescent Organic Ligand and Complexes of Trivalent Rare Earth[J]. Spectrochim Acta , Part A ,2007,66(3):667-671.
[3] Kaur G,Dwivedi Y,Rai S B. Synthesis, Structural, Thermal and Optical Studies of Rare Earth Coordinated Complex:Tb(Sal) 3 Phen[J]. Mater Chem Phys ,2011,130(3):1351-1356.
[4] Suo Q L,Lu F,Shi J W, et al . Studies on Synthesis and Fluorescent Property of Rare Earth Complexes RE(ABMF) 2 AA and Copolymers RE(ABMF) 2 AA-co-MMA[J]. J Rare Earths ,2009,27(1):28-32.
[5] Guo L,Wu S Z,Zeng F, et al . Synthesis and Fluorescence Property of Terbium Complex with Novel Schiff-base Macromolecular Ligand[J]. Eur Polym J ,2006,42(7):1670-1675.
[6] Liu D,Wang Z G,Yu H, et al . Fluorescence Properties of Novel Rare Earth Complexes Using Carboxyl-containing Polyaryletherketones as Macromolecular Ligands[J]. Eur Polym J ,2009,45(8):2260-2268.
[7] Liu X Y,Hu Y L,Wang B Y, et al . Synthesis and Fluorescent Properties of Europium-polymer Complexes Containing 1,10-Phenanthroline[J]. Synth Met ,2009,159(15/16):1557-1562.
[8] Huang H L,Zhong C F,Zhang H L, et al . Synthesis and Photophysical Properties of Novel Polymeric Eu(Ⅲ) Complex with Bicoordination Ligand[J]. J Lumin ,2008,128(11):1863-1866.
[9] Tang H L,Ma Z,Yang J, et al . Flexible Polyarylene Ether Nitrile Containing Pendant Carboxyl Groups/Eu(Ⅲ) Fluorescentfilms with High Thermal Stability and Mechanical Strength[J]. Mater Lett ,2011,65(23/24):3450-3453.
[10] Yan B,Wang Q M. Molecular Fabrication and Photoluminescence of Novel Terbium Co-polymer Using 4-Vinyl Pyridine as the Efficient Second Ligand[J]. Opt Mater ,2007,30(4):617-621.
[11] Liu D,Wang Z G. Novel Polyaryletherketones Bearing Pendant Carboxyl Groups and their Rare Earth Complexes:Synthesis and Characterization[J]. Polymer ,2008,49(23):4960-4967.
[12] WangL H,Chen Z K,Kang E T, et al . Synthesis and Magnetic Properties of the Ho(BA) 2 AA Complex Monomer and Its Copolymer with MMA[J]. Synth Met ,2001,118(1):39-43.
[13] Yan C H,Yu C J,Hu H H, et al . Preparation and Properties of RE 3+ Doped Luminescent Co-polymer by Solution Copolymerization[J]. J Rare Earths ,2009,27(5):761-766.
[14] Gao B J,Fang L,Zhang R X, et al . Preparation of Aromatic Carboxylic Acid-Functionalized Polysulfone and Preliminary Exploration of Florescence Emission Character of Formed Polymer-rare Earth Complexes[J]. Synth Met ,2012,162(5/6):503-510.
[15] Gao B J,Zhang W,Zhang Z-G, et al . Preparation of Polymer rare Earth Complex Using Salicylic Acid-containing Polystyrene and Its Fluorescence Emission Property[J]. J Lumin ,2012,132(8):2005-2011.
[16] Gao B J,Qiao Z W,Chen T. Structure and Photoluminescence Property of Complexes of Aromatic Carboxylic Acid-functionalized Polysulfone with Eu(Ⅲ) and Tb(Ⅲ)[J]. Mater Chem Phys ,2014,143(3):1119-1130.
[17] Gao B J,Fang L,Men J Y. Studies on Preparation, Structure and Fluorescence Emission of Polymer-rare Earth Complexes Composed of Aryl Carboxylic Acid-functionalized Polystyrene and Tb(Ⅲ) Ion[J]. Polymer ,2012,53(21):4709-4717.
[18] Lee J C,Jeong Y-K,Kim J-M, et al . Sensitized Luminescence of Eu(Ⅲ) Complexes with Schiff-base and 1,10-Phenanthroline:Role of Schiff-base as a Sensitizer[J]. Spectrochim Acta , Part A ,2014,124:256-264.
[19] Al-Rasbi N K,Adams H,Suliman F O. Synthesis, Structure and Tunable White-light Emission of Dinuclear Eu(Ⅲ) Schiff Base Complex[J]. Dyes Pigm ,2014,104:83-88.
[20] SHEN Yanling,YANG Yunfeng,GAO Baojiao, et al . Synthesis of Linear Chloromethylated Polystyrene with 1,4-Bis(chloromethoxyl)butane as Chloromethylation Reagent[J]. Acta Polym Sin ,2007,(6):559-565(in Chinese). 申艳玲,杨云峰,高保娇,等. 以1,4-二氯甲氧基丁烷为氯甲基化试剂合成线型氯甲基化聚苯乙烯[J]. 高分子学报,2007,(6):559-565.
[21] WANG Mingjuan,GAO Baojiao,DU Junmei. Preparation of Naphthoic Acid-functionalized Polysulfone and Preliminary Exploration of Fluorescence Emission of Formed Polymer-Rare Earth Eu(Ⅲ) Complexes[J]. Chinese J Appl Chem ,2013,30(3):283-289(in Chinese). 王明娟,高保娇,杜俊玫. 萘甲酸功能化聚砜的制备及其与Eu(Ⅲ)稀土离子配合物的荧光发射特性[J]. 应用化学,2013,30(3):283-289.
[22] Taha Z A,Ajlouni A M,Al-Hassan K A, et al . Syntheses, Characterization, Biological Activity and Fluorescence Properties of Bis-(salicylaldehyde)-1,3-propylenediimine Schiff Base Ligand and Its Lanthanide Complexes[J]. Spectrochim Acta , Part A ,2011,81(1):317-323.