几种席夫碱功能化的聚合物及其稀土配合物的制备与性能研究

发布时间：2018-01-03 17:18

本文关键词：几种席夫碱功能化的聚合物及其稀土配合物的制备与性能研究　出处：《兰州理工大学》2016年硕士论文　论文类型：学位论文

【摘要】：稀土有机配合物的发光性质在众多领域都得到广泛的应用,正被越来越多的研究者所关注。本文以合成新型的席夫碱功能化聚合物及其稀土配合物为中心,构筑了三个系列含有席夫碱功能基元的聚合物及其稀土离子配合物,并研究了其发光性能。主要研究工作和实验结果如下:1、以苯乙烯、丙烯酸丁酯、水杨醛和水合肼为原料,制备了一系列含有席夫碱功能侧基的聚苯乙烯/丙烯酸丁酯(PSCBS),以其作为大分子配体与稀土Eu3+/Y3+进行配位反应,合成具有预设计结构和功能的稀土/高分子席夫碱配合物,并利用红外光谱、紫外-可见吸收光谱、元素分析和热重分析对配体及配合物的组成、结构和热稳定性进行了表征和研究,利用荧光光谱对配合物的发光性能进行了研究。研究表明,所制备配合物具有良好的溶解性、成膜性及热稳定性。在聚合物侧链上引入席夫碱功能基团后,可赋予聚合物良好的配位能力,席夫碱基团中的氮原子,羰基中的氧原子和羟基中的氧原子均参与配位反应;配体在紫外区有强烈的吸收,主要表现为苯环结构中的π→π*跃迁吸收和席夫碱结构中-C=N-的n→π*吸收;配合物在可见光激发下发射出配体和Eu3+的共发光特征谱线,且在苯乙烯单体与丙烯酸丁酯单体摩尔比为1:1时Eu3+的特征荧光强度达到最大值。2、以对苯二甲醛、水合肼和水杨醛为原料,通过缩聚反应,设计制备了不同聚合度、以缩芳香醛类席夫碱为主链的共轭型聚合物(PTF),并以其作为大分子配体,Eu3+/Y3+作为中心离子,成功制备了稀土/高分子席夫碱配合物PTF-Eu(III)/Y(III)。利用红外光谱,紫外-可见吸收光谱、元素分析和热重分析对配体及配合物的组成、结构和热稳定性进行了表征和研究,利用荧光光谱对配合物的发光性能进行了研究。研究表明,所制备的稀土/高分子席夫碱配合物具有较好的热稳定性和溶解性;在主链上引入共轭的席夫碱结构使得聚合物的能带特征发生较大变化,有利于提高聚合物的配位能力;配体在紫外区有较强的吸收,主要表现为苯环结构中的π→π*跃迁吸收和席夫碱结构中-C=N-的n→π*吸收;配合物在可见光激发下发射出配体和Eu3+的共发光特征谱线,且在设计聚合度为10时,配合物的荧光强度达到最大值。3、以对苯二甲酸二甲酯、水合肼和水杨醛为原料,通过缩聚反应,设计制备了含有水杨醛功能端基、以聚酰腙类席夫碱为主链的聚合物配体(PBT),以其作为大分子配体与稀土Eu3+/Y3+进行配位反应,成功制备了稀土/高分子席夫碱配合物PTF-Eu(III)/Y(III),并利用红外光谱,紫外-可见吸收光谱、元素分析和热重分析对配体及配合物的组成、结构和热稳定性进行了表征和研究,利用荧光光谱对配合物的发光性能进行了研究。研究表明,所制备的稀土高分子配合物具有较好的溶解性和热稳定性;聚合物链端的水杨醛基团和主链的酰腙结构能有效提高配合物的配位能力;配体在紫外区有较强的吸收,主要表现为苯环结构中的π→π*跃迁吸收和席夫碱结构中-C=N-的n→π*吸收;配合物在可见光激发下发射出配体和Eu3+的共发光特征谱线,表明配体PBT与稀土离子之间发生了有效的能量传递,配合物PBT-Eu(III)/Y(III)表现出良好的荧光性能。
[Abstract]:The luminescence properties of rare earth organic complexes have been widely used in many fields, being more and more attention by researchers. In this paper the synthesis of Novel Schiff functionalized polymers and complexes of rare earth as the center, built three series containing Schiff base polymer functional element and rare earth ion complexes. And their photoluminescence properties were investigated. The main research work and results are as follows: 1, using styrene, butyl acrylate, salicylaldehyde and hydrazine hydrate as raw materials, a series of Schiff base containing functional side groups of polystyrene / butyl acrylate (PSCBS), was prepared by coordination reaction as macromolecular ligand and Eu3+/Y3+ rare earth rare earth / polymer Schiff Base Complexes synthesized with pre designed structure and function, and the use of infrared spectroscopy, UV Vis absorption spectroscopy, elemental analysis and thermogravimetric analysis on the composition of the complex ligand and structure. And the thermal stability were characterized and studied. The luminescent properties of the complexes were studied by fluorescence spectroscopy. The results show that the prepared complexes have good solubility and film-forming property and thermal stability. Schiff introduced functional groups in the polymer side chain, can give good coordination polymers a capacity of nitrogen atom Schiff base group, oxygen atom and hydroxyl carbonyl oxygen atoms in the ligand are involved in the coordination reaction; have strong absorption in the ultraviolet region, mainly for PI, pi * benzene ring structure in N, pi * -C=N- absorption and Schiff base structure in absorption; complexes in the visible light emitted from the ligand and Eu3+ co luminescence characteristic lines, and in the styrene monomer and acrylate monomer molar ratio is 1:1 when the characteristics of the fluorescence intensity of Eu3+ reached the maximum value of.2, with two of benzene formaldehyde, hydrazine hydrate and salicylaldehyde as raw material, through shrinkage Polymerization, design and preparation of different degree of polymerization, the conjugated polymer backbone by condensation of aromatic aldehydes Schiff base (PTF), and used as a macromolecular ligand and Eu3+/Y3+ as central ion, successful preparation of rare earth / polymer Schiff base complexes PTF-Eu (III) /Y (III) use. Infrared spectroscopy, UV Vis absorption spectroscopy, elemental analysis and thermal analysis of complexes of the ligand and the composition, structure and thermal stability were characterized and studied. The luminescent properties of the complexes were studied by fluorescence spectroscopy. The results show that the prepared rare-earth / polymer complexes with Schiff base the thermal stability and good solubility; Schiff base structure is introduced in the main chain of the conjugate band characteristics change of polymer, polymer can improve the coordination ability; ligand has strong absorption in the UV region, mainly for PI, pi * in the benzene ring structure N, pi * -C=N- absorption and Schiff base structure in absorption; complexes under visible light emitted from the ligand and Eu3+ co luminescence characteristic lines, and in the design of polymerization degree is 10, the fluorescence intensity of the complex was reached the maximum value of.3 to two, terephthalic acid methyl ester, hydrazine hydrate and water Yang aldehyde as raw material, through the condensation reaction design and preparation containing salicylaldehyde functional groups, poly hydrazone Schiff base ligands for the polymer backbone (PBT), of the coordination reaction as macromolecular ligand and rare earth Eu3+/Y3+, the successful preparation of rare earth / polymer Schiff base complexes (PTF-Eu III) /Y (III), and the use of infrared spectroscopy, UV Vis absorption spectroscopy, elemental analysis and thermal analysis of complexes of the ligand and the composition, structure and thermal stability were studied and luminescent properties of the complexes were studied by fluorescence spectroscopy. The results show that the prepared The rare earth polymer complexes have good solubility and thermal stability of the hydrazone; structure of polymer chain end salicylaldehyde groups and the main chain can effectively improve the complexes; ligand has strong absorption in the UV region, mainly for PI, pi * benzene ring structure in N, pi * -C=N- transition the absorption and Schiff base structure in absorption; complexes under visible light emitted from the ligand and Eu3+ co luminescence spectral lines show that the effective energy transfer between rare earth ions and ligand PBT complexes, PBT-Eu (III) /Y (III) fluorescence showed good performance.

【学位授予单位】：兰州理工大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：O641.4

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