【作者】 刘兴妤；

【导师】 苏致兴；

【作者基本信息】 兰州大学 ， 高分子化学与物理， 2008， 博士

【摘要】 稀土高分子发光材料是指稀土离子掺杂或键合于高分子中的功能性聚合物。稀土金属离子作为一种有效的发光中心，在无机和有机发光材料中已有广泛应用。然而稀土无机材料存在着难加工成型、价格高等问题，稀土有机小分子配合物则存在稳定性差等问题，这些因素限制了稀土发光材料更为广泛地应用。高分子材料本身具有稳定性好、来源广、容易加工成型等特点，将稀土离子引入到高分子基质中制成稀土高分子发光材料，其应用前景将十分广阔。本论文根据所合成的稀土小分子配合物的性质分别选用水溶性高分子（包括天然高分子）和油溶性单体及相应高分子作为原料，将稀土离子掺杂或键合到这些高分子基质中，实现了它们的高分子化。采用核磁（NMR），质谱（MS），红外光谱（FT-IR），元素分析（EL）、差示扫描量热法（DSC），可见紫外分光光度仪（UV），凝胶渗透色谱法（GPC）和荧光光谱等方法对稀土小分子配合物和稀土高分子发光材料的结构和性能进行了表征，并系统研究了此类高分子的荧光性质。（1）论文选用聚乙烯吡咯烷酮（PVP）、聚乙烯醇（PVA）、聚甲基丙烯酸甲酯（PMMA）作为高分子基质材料，采用掺杂的方法将铕／α-噻吩甲酰三氟丙酮／N-甲基吡咯烷酮[Eu（TTA）₃·2NMP]三元配合物引入高分子基质材料中。研究了这些成膜材料对铕／α-噻吩甲酰三氟丙酮／N-甲基吡咯烷酮[Eu（TTA）₃·2NMP]三元配合物发光性能的影响。荧光测试结果表明：不论三元配合物／聚合物是溶液状态，还是三元配合物／聚合物膜材料，它们的荧光强度均大于三元配合物的荧光强度。高分子薄膜的荧光强度比相应溶液的荧光强度高2⁵倍。红外光谱研究表明配合物与这些成膜材料之间都存在相互作用。做成材料的荧光强度远高于Eu／有机小分子配合物的荧光强度，并且稳定性好。同时，论文还选用水溶性高分子聚乙烯醇（PVA）、聚乙烯吡咯烷酮（PVP）、聚丙烯酰胺（PAM）、淀粉（Starch）、环糊精（β-Cyclodextrin）作为高分子基质材料，采用掺杂的方法将以诺氟沙星药物分子为配体的铽（Ⅲ）配合物B引入其中。研究了其二元配合物在水溶性高分子中和相应的高分子成膜材料的荧光性能。荧光测试结果表明：固体配合物B的荧光强度只是高于B-PAM的荧光强度，与其它成膜材料的荧光强度相比都要弱。也就是说，淀粉、PVA、环糊精和PVP都对Tb³⁺发光产生的增强效应。（2）论文合成了含稀土离子铕的有机小分子配合物Eu（TTA）₂AA单体，并分别与甲基丙烯酸甲酯（MMA）和乙烯基咔唑（NVK）单体进行共聚合反应，得到了一系列Eu含量不同的键合型Poly（MMA-co-Eu（TTA）₂AA）和Poly（NVK-co-Eu（TTA）₂AA）稀土发光共聚高分子。研究表明：键合型稀土发光共聚高分子的荧光强度随Eu含量的增加而增加，未出现浓度猝灭现象；在掺杂型聚合物中Eu（TTA）₂AA／PMMA和Eu（TTA）₂AA／PVK中，由于配合物的聚集，激子迁移过程以浓度猝灭占优势，从而导致聚合物的荧光强度随Eu含量的增加而减弱。（3）论文采用不饱和双键修饰法，以5-丙烯酰胺基-1，10-邻菲罗啉（AP）为配体，并采用两种不同的合成方法（1．先配合再聚合；2．先聚合再配合）分别合成得到两种不同的键合型稀土高分子发光材料。（1）以5-丙烯酰胺基-1，10-邻菲罗啉为配体，先与稀土离子铕配位得到含铕的配合物。并将它与甲基丙烯酸甲酯进行共聚得到稀土配合物共聚高分子；（2）以5-丙烯酰胺基-1，10-邻菲罗啉为单体与甲基丙烯酸甲酯的共聚物为高分子配体，配位基为芳环上的氮原子，并以N-甲基吡咯烷酮小分子配体协同反应，与Eu³⁺配位形成了三元光致发光稀土高分子配合物，并对以上两种方法进行比较。结果表明，采用方法（1）得到的稀土配合物共聚高分子结构稳定，稀土离子Eu³⁺分布均匀，荧光强度强且稳定。而采用方法（2）制得的稀土高分子配合物虽然也有荧光，但荧光很弱，需要加入第二配体才可能使Eu³⁺的荧光得到提高。论文研制了五种稀土发光高分子材料，它们具有潜在的应用前景，可运用于光致发光器件中。更多还原

【Abstract】 Luminescent rare earth complexes have attracted considerable attention to organic electroluminescent （EL） devices as well as for optical microcavity emitters owing to their inherent extremely sharp emission bands and potentially high internal quantum efficiency. However, there are many problems for the rare earth complexes that have small molecular weight such as the instability in organic solution and poor compatibility with other materials. Thus, to extend the application of rare earth-containing polymers has attracted attention in the past decade. In comparison with small molecular weight rare earth complexes, besides the advantage of the desired mechanical flexibility, polymer-based rare earth luminescent materials can be soluble or fused processable, which is attractive for optical and electronic applications.There are two techniques which are usually used to synthesize rare earth-containing polymers materials. One is the copolymerization of rare earth-containing monomers and polymeric monomers.The other is the direct reaction of the polymer ligands with rare earth ions.In this paper, the rare earth complexes serving as chromophores were attached successfully on polymers through two different methods mentioned above. The synthesized complexes and rare earth-containing polymers were characterized by the methods of nuclear magnetic resonance （NMR）, mass spectrography （MS）, infrared spectra （IR）, ultra-violet-visible spectra （UV）, element analysis （EA）, differential scanning calorimetry （DSC）, gel permeation chromatography （GPC） and fluorescence spectra, respectively.（1） The ternary complex Eu/Thenoyltrifluoroaceton/N-methyl-2-pyrrolidone [Eu （TTA）₃·2 NMP] was doped into three types of polymer including Polyvinylpyrrolidone （PVP）, Polyvinyl alcohol （PVA） and Polymethyl methacrylate （PMMA）. The luminescence properties of the blends was studied in this paper. According to the results, it showed that the fluorescence intensity of the polymer doping with ternary complex was stronger than that of ternary complex itself, no matter what the ternary complex was both in solution and film state. The fluorescence intensity of polymer film was 2⁵ times higher than that of solution. And the FT-IR spectra showed that there was interaction existing between the rare earth complex and film material. The polymer material had higher fluorescence intensity than that of small molecular weight rare earth complexes and was more stable.The luminescence properties of the doping materials of Tb/Norfloxacin [Tb（NFLX）₃·8H₂O] with five types of water soluble polymers including polyvinylpyrrolidone （PVP）, polyvinyl alcohol （PVA）, polyacrylamide （PAM）,β-Cyclodextrin and Starth was studied. According to the results, it exhibitted that the fluorescence intensity of the doped-polymer except B-PAM was stronger than the binary complex. It also indicated that Starch, PVA,β-Cyclodextrin and PVP could enhance the fluorescence intensity of Tb³⁺.（2） An europium-containing polymer Poly（MMA-co-Eu（TTA）₂AA） was successfully prepared via copolymerization of MMA with the organic complex containing Eu（TTA）₂AA, which was synthesized via the reaction among EuCl₃, TTA, AA and MMA. Compared with the doped-polymer Eu（TTA）₂AA/PMMA, the fluorescence intensity of the copolymer Poly（MMA-co-Eu（TTA）₂AA） increased with the concentration of Eu increasing and there was no concentration quenching effect while the fluorescence intensity of Eu（TTA）₂AA/PMMA decreased upon increasing the concentration of Eu once the concentration of Eu was higher than 3.67% in the Eu（TTA）₂AA/PMMA. The decrease of fluorescence intensity of Eu（TTA）₂AA/PMMA was due to the aggregation of complex, excitonic transfer and concentration quenching. From the analysis of XRD, we found that Eu（TTA）₂AA could regularly be dispersed uniformly in the polymer complex and emit strong fluorescence.An europium-containing polymer Poly（NVK-co-Eu（TTA）₂AA） was successfully prepared via copolymerization of NVK with the organic complex containing Eu（TTA）₂AA, which was synthesized via the reaction among EuCl₃ ,TTA, AA and NVK. Compared with the doped-polymer Eu（TTA）₂AA/PVK, the fluorescence intensity of copolymer Poly（NVK-co-Eu（TTA）₂AA） increased with the concentration of Eu and there was no concentration quenching effect. From the analysis of XRD, we found that Eu（TTA）₂AA could regularly disperse in the polymer complex and emit strong fluorescence. （3） In this paper, 5-acrylamido-1, 10-phenanthroline （AP） was synthesized, then the luminescence material containing Eu-polymer complexes was obtained by two methods. Compared with the rare earth-containing polymer synthesied by the reaction of rare earth with the polymer ligand （Poly（MMA-co-AP））, the one prepared by copolymerization of polymeric monomer with small molecular complex (Poly（MMA-co-Eu（AP）₃） had high and stable fluorescence intensity with the Eu contents was incresed to 0.31%. By comparing the two materials prepared via different methods, we have set down the useful basement for the study of the luminescence material containing Eu-polymer complexes.In particularly, the typical features of rare earth-containing polymers prepared in this dissertation would make them very suitable to be used as polymer electroluminescence materials.更多还原