【作者】 马松涛；

【导师】 方少明；

【作者基本信息】 郑州轻工业大学 ， 材料学， 2010， 硕士

【摘要】 丙烯酸酯类聚氨酯（PUA）材料具有耐磨、耐磨蚀、耐高温、韧性好、高透明性、高精度等优点,在材料领域已经被广泛的应用。由于其独特分子结构和可控的聚合反应,最后可以实现材料的功能化。稀土元素因具有独特的电子结构,丰富的电子能级,决定其具有较好的荧光性能或磁性能。但是稀土离子存在发光效率低的问题,为了解决这一问题,选择高吸光系数的有机配体。这种高吸光系数的有机配体与稀土离子形成稀土配合物后,能够将吸收的光能有效的传递给稀土离子,使得稀土离子的特征荧光增强,进而提高稀土离子的发光效率。这种有机稀土配合物已经成为一类重要的荧光材料。本论文以丙烯酸酯类聚氨酯材料为基质,采用掺杂法和键合法两种途径来制备稀土聚氨酯材料。（1）通过高温水热法制备了稀土配合物[Tb（L¹）（phen）]_∞,并对晶体结构经行了解析,其中L¹:5-羟基间苯二甲酸阴离子配体,phen:邻菲罗啉。将该配合物与丙烯酸酯类聚氨酯大单体直接掺杂,经固化制得稀土TbIII配合物/丙烯酸酯类聚氨酯绿色荧光材料,并对该复合材料热性能,力学性能,荧光性能以及动态力学性能等进行了表征。研究表明:在399 nm激发光的照射下,复合材料具有较好的绿色荧光性能,且随着稀土元素含量的增加,荧光性能增强,其中当稀土含量增加到7 %时,材料仍具有较强的绿色荧光,没出现荧光猝灭现象;材料的耐热性能有所提高;稀土含量的增加对材料的力学性能影响较小;玻璃化温度随着稀土含量的提高先增大后减小,当稀土含量达到1.5 %时,玻璃化温度达到最大。（2）通过高温水热法制备出稀土配合物[Dy₂（L²）₃（H₂O）₄]∞,其中L₂:2,6-二羟基异烟酸阴离子配体,并解析了晶体结构。将该配合物直接与丙烯酸酯类聚氨酯掺杂,制备稀土DyIII配合物/丙烯酸酯类聚氨酯复合材料,并对复合材料的热力学性能、内部结构、荧光性能进行表征。结果表明:该配合物在基质中以200⁸00 nm颗粒均匀分散;该材料具有良好的热稳定性能,在激发波长469 nm激发下,发射光谱在515 nm荧光强度达到最大,且随着稀土配合物含量的增高,荧光强度不断增强,没有出现荧光猝灭的现象。（3）通过试管扩散法合成了一种带有可反应官能团（羟基）稀土配合物,该配合物的化学式为:{[Sm（L³）₃（phen）]₂（dmpy）（C₂H₅OH）₂（H₂O）₂}_∞,其中L³:对羟基苯丙烯酸基阴离子配体,dmpy:2,6-二甲基吡啶。将该配合物与丙烯酸酯类聚氨酯大单体键合制得稀土SmIII配合物/PUA复合材料,并研究不同稀土配合物含量对复合材料的热稳定性能、荧光性能和力学性能的影响。为了改善材料的透光性,做了另外一组对比试验,引入“万能溶剂”—DMF。先将配合物溶解在DMF中再将其掺杂到基材当中。对比两种不同方法制备出来的材料各种性能差异。结果表明:第二组对比试验制备出来的复合材料较第一组试验制备出来的复合材料透光率明显提高,而且没有影响材料的荧光效果,但是材料的热力学性能有所下降。（4）以5-氨基间苯二甲酸为配体,通过试管扩散法,制备了一种稀土铕配合物{[Eu（H₂L⁴）₂（H₂O）₅]（H₄L⁴）}∞,利用该配合物中的氨基作为活性基团,通过大单体制备技术,制备出新的键合型丙烯酸类聚氨酯光致发光材料,并对材料的荧光、热重等性能进行了测试。研究表明:在349 nm波长激发下,稀土配合物及发光材料在616 nm处发出较强的特征荧光。甚至当稀土配合物含量达到8 %时,依然没有发生荧光猝灭现象。且随着稀土配合物含量的增加,复合材料的外推起始热降解温度较纯的PUA材料逐渐提高。更多还原

【Abstract】 The material of polyurethane-acrylate （PUA） has been applied extensively in the fields of engineering materials due to its characteristics of corrosion-resistant, high temperature resistance, good toughness, high transparency, high precision, etc. Various PUA materias with different mechanical properties can be obtained by exact designing molecular structure of product. Finally, the function of the materials was realized.The rare earth elements have unique electronic structure and rich electronic energy levels which determine them have good fluorescence properties or magnetic properties. But the low luminescence efficiency of rare earth ions is a problem. In order to solve this problem, we chose the organic ligand which has a high absorption coefficient to form the organic complex. The organic ligand can absorb light energy. Then the energy can be passed to the rare earth ions which can emit characteristic fluorescence, thus an important class of fluorescent material is obtained. Considering these respects mentioned above, in this dissertation, polyurethane-acrylate material were selected as matrices incorporating the rare earth complexes with different predestined organic ligands to construct novel functional composites by employing doping-type and bonding-type, respectively. The main contents including four chapters are as follows:（1） The rare earth complexes [Tb（L¹）（phen）]∞was prepared through high-temperature hydrothermal method, in which L1 is 5-hydroxy-isophthalic acid-based anionic ligands, phen is phenanthroline. The crystal structure of the obtained complex was analyzed. The rare earth TbIII / polyurethane green fluorescent composite materials were prepared by the complex being doped into PUA. The properties of the composite materical were characterized, such as thermal properties, mechanical properties, fluorescence properties and dynamic mechanical properties. The results showed that composite material has good green fluorescence properties. Fluorescence properties of composite material become more and more strongger with the RE content increasing. When the rare earth content is 7%, the composite material can still send a strong green fluorescence, no fluorescence quenching. Heat resistance of materials has increased with the increase of RE content. The glass transition temperature increases at first and then decreases with the increase of RE content. When the rare earth content is 1.5 %, the glass transition temperature reached maximum.（2） The rare earth complex [Dy₂（L²）₃（H2O）4]_∞was synthesized by high temperature hydrothermal, in which L² is citrazinic acid-based anionic ligands, and its crystal structure was analysed. The complex was doped with the PUA directly to prepare the rare earth complex/PUA composite material. The thermodynamic properties, fluorescent properties and internal structure of composite materials were characterized. The results reveal that the complex is dispersed in PUA at about 200⁵00 nm. The material has the good thermal stability. Materiales were excitated by the excitation wavelength 469 nm light. In emission spectra, fluorescence intensity reached the maximum at the 515 nm. Fluorescence intensity grew with the increased content of rare earth complex. There was no fluorescence quenching phenomenon.（3） The rare earth complex {[Sm（L³）₃（phen）]₂（dmpy）（C₂H₅OH）₂（H₂O）₂}_∞with a reaction of a functional group （hydroxyl） can be synthesized by the vitro diffusion method, in which L³ is p-hydroxy acrylic acid-based anionic ligands and dmpy is 2,6-lutidine. The good fluorescence of the complex / PUA was obtained by chemical bond. Composite materials with the different content rare earth complex were investigated by light transmittance, thermal stability and fluorescence properties. Materials were excitated by the excitation wavelength 474 nm light. In emission spectra, fluorescence intensity reached the maximum at the 597 nm. In order to improve the material transmittance to do another set of comparative tests, DMF was introduced, which is "universal solvent". The complex first was dissolved in DMF, then bonding with PUA. The results showed that the transmittance of composite materials has further improved by using the DMF. What’s more, DMF did not affect the fluorescence of materials, but the thermal property of materials has declined.（4） The rare earth complex {[Eu（H₂L⁴）₂（H₂O）₅]（H₄L⁴）}_∞was synthesized using 5-amino-isophthalic acid as the ligand. The active functional group （–NH₂） in the ternary complex was used to react with -NCO functional group of IPDI. By means of macromonomer technique, a novel photoluminescent material containing both the rare earth complex and PUA was obtained. The structure and properties of materials were characterized by FTIR, thermogravimetric analysis and fluorescence spectroscopy. Both the complex and photoluminescent polymer material emitted characteristic fluorescence at 616 nm after excitation at a wavelength of 349 nm. The fluorescent quenching wouldn’t appear when the content of complex reached 8 %. Forthermore, the initial degradation temperature increased with increasing the content of complex.更多还原