功能高分子微球稀土络合体及其功能复合材料
摘要
本文利用无皂乳液聚合法合成了苯乙烯(St)和甲基丙烯酸(MAA)共聚(P(St-co-MAA))功能高分子微球。然后，利用P(St-co-MAA)微球、乙酰丙酮(acac)和邻菲哕啉(phen)作为配体制备了稀土高分子三元络合物。最后，将此络合物掺杂到甲基丙烯酸甲酯和甲基丙烯酸共聚物(P(MMA-co-MAA))中，制备出稀土高分子络合物膜材料。
用光散射仪和透射电镜表征了功能高分子微球的粒径大小和形态，用红外光谱，荧光光谱等研究了功能高分子微球、稀土三元络合物和掺杂稀土络合物膜的结构及荧光性能。结果表明：
1．采用无皂乳液聚合法制备的P(St-co-MAA)功能高分子共聚微球呈规则球状，粒径为纳米级且具有单分散性。
2．制备的稀土P(St-co-MAA)微球络合物，具有优良的荧光性能。在紫外光照射下，均能发出相应稀土离子的特征荧光。这是因为P(St-co-MAA)微球，acac和phen作为配体能够有效的将能量传递给发光中心(稀土离子)。适当增加P(St-co-MAA)为球的含量还可以增强稀土络合物的发光强度。
3．掺杂稀土高分子络合物膜，具有了更好的发光性能。这说明P(MMA-co-MAA)基体与稀土离子之间存在有效的能量传递，而且在掺杂过程中，P(MMA-co-MAA)还能够更好的分散开稀土离子，使得每一微小络合物都处于不同的环境，这也会促使体系产生超敏跃迁现象。当络合物含量较高时，稀土络合物膜并没有出现“浓度淬灭”现象，这说明掺杂前稀土离子的络合较充分，在络合物中已具有良好的分散性。另外，掺杂后的稀土络合物膜还具有了良好的力学、透光性能，从而大大增加了其应用性。
In this paper, poly(styrene-co-methacrylicacid)[P(St-co-MAA)] functional nanospheres were synthesized by emulsifier-free emulsion copolymerization. Then ternary complexes of RE~(3+) with P(St-co-MAA) nanospheres, acetylacetone(acac) and 1,10-phenanthroline(phen) as ligands were prepared. In the end, the RE~(3+) film was prepared by doping ternary complexes of RE~(3+) in P(MMA-co-MAA).Light scattering apparatus, transmission electron microscopy(TEM) were used to determine the size and morphology of P(St-co-MAA) nanospheres. FT-IR spectra and fluorescence spectra were applied to characterize the configuration and property of functional nanospheres, ternary complexes of RE~(3+) and RE~(3+) complex film. The results were as follows:1. P(St-co-MAA) nanospheres with monodisperse size distribution were prepared by emulsifier-free emulsion copolymerization of styrene and methacrylicacid.2. The ternary complexes of RE~(3+) could emit their strong typical fluorescence under ultraviolet (UV) radiation, which resulted from efficient energy transfer from P(St-co-MAA) nanospheres, acac and phen to the central ions(RE~(3+)). The fluorescent intensity could be enhanced by increasing the content of P(St-co-MAA) nanospheres.3. The ternary complexes of RE~(3+) film displayed better fluorescent property than RE~(3+) complexes, which resulted from efficient energy transfer from P(MMA-co-MAA) to RE~(3+) . "Concentration quench effect" didn't appear with a relative high content of RE~(3+), which indicated that the complex reaction of RE~(3+) was carried out thoroughly before doping. The RE~(3+) possessed excellent dispersion in the complexes. In addition, the application of these materials were improved since RE~(3+) complexes film had fine mechanics property and transparency.
用光散射仪和透射电镜表征了功能高分子微球的粒径大小和形态，用红外光谱，荧光光谱等研究了功能高分子微球、稀土三元络合物和掺杂稀土络合物膜的结构及荧光性能。结果表明：
1．采用无皂乳液聚合法制备的P(St-co-MAA)功能高分子共聚微球呈规则球状，粒径为纳米级且具有单分散性。
2．制备的稀土P(St-co-MAA)微球络合物，具有优良的荧光性能。在紫外光照射下，均能发出相应稀土离子的特征荧光。这是因为P(St-co-MAA)微球，acac和phen作为配体能够有效的将能量传递给发光中心(稀土离子)。适当增加P(St-co-MAA)为球的含量还可以增强稀土络合物的发光强度。
3．掺杂稀土高分子络合物膜，具有了更好的发光性能。这说明P(MMA-co-MAA)基体与稀土离子之间存在有效的能量传递，而且在掺杂过程中，P(MMA-co-MAA)还能够更好的分散开稀土离子，使得每一微小络合物都处于不同的环境，这也会促使体系产生超敏跃迁现象。当络合物含量较高时，稀土络合物膜并没有出现“浓度淬灭”现象，这说明掺杂前稀土离子的络合较充分，在络合物中已具有良好的分散性。另外，掺杂后的稀土络合物膜还具有了良好的力学、透光性能，从而大大增加了其应用性。
In this paper, poly(styrene-co-methacrylicacid)[P(St-co-MAA)] functional nanospheres were synthesized by emulsifier-free emulsion copolymerization. Then ternary complexes of RE~(3+) with P(St-co-MAA) nanospheres, acetylacetone(acac) and 1,10-phenanthroline(phen) as ligands were prepared. In the end, the RE~(3+) film was prepared by doping ternary complexes of RE~(3+) in P(MMA-co-MAA).Light scattering apparatus, transmission electron microscopy(TEM) were used to determine the size and morphology of P(St-co-MAA) nanospheres. FT-IR spectra and fluorescence spectra were applied to characterize the configuration and property of functional nanospheres, ternary complexes of RE~(3+) and RE~(3+) complex film. The results were as follows:1. P(St-co-MAA) nanospheres with monodisperse size distribution were prepared by emulsifier-free emulsion copolymerization of styrene and methacrylicacid.2. The ternary complexes of RE~(3+) could emit their strong typical fluorescence under ultraviolet (UV) radiation, which resulted from efficient energy transfer from P(St-co-MAA) nanospheres, acac and phen to the central ions(RE~(3+)). The fluorescent intensity could be enhanced by increasing the content of P(St-co-MAA) nanospheres.3. The ternary complexes of RE~(3+) film displayed better fluorescent property than RE~(3+) complexes, which resulted from efficient energy transfer from P(MMA-co-MAA) to RE~(3+) . "Concentration quench effect" didn't appear with a relative high content of RE~(3+), which indicated that the complex reaction of RE~(3+) was carried out thoroughly before doping. The RE~(3+) possessed excellent dispersion in the complexes. In addition, the application of these materials were improved since RE~(3+) complexes film had fine mechanics property and transparency.
引文
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