【作者】 周立明；

【导师】 张留成； 闫卫东； 方少明；

【作者基本信息】 河北工业大学 ， 材料学， 2009， 博士

【摘要】 本文以聚氨酯丙烯酸酯大分子单体（MUA）及其聚合物（PUA）的合成研究为基础,在设计合成具有新颖结构的稀土配合物的同时,创造性的将稀土配合物引入到聚氨酯丙烯酸酯大单体的聚合体系中,构筑了一系列具有良好光致发光性能的透明稀土高分子材料,并对材料的结构、性能进行了详细的研究探讨。1.利用水热法和常规溶液反应法,设计合成了以下不同配体系列的九种稀土配合物:[Tb(C₁₅H₉O₂)₃(C₁₀H₈N₂)]₂ ( C₁₅H₉O₂ : 9-蒽甲酸; C₁₀H₈N₂ : 2,2-联吡啶)（ 1 ）、{[Sm(C₁₆H₈O₄)₂（H₂O）₂](C₇H₁₀N)（H₂O）_1.75}_∞(C₁₆H₈O₄:9,10-蒽二甲酸;C₇H₁₀N:质子化的2,6 -二甲基吡啶) （ 2 ）、Eu（C₃H₃O₂）₃ （ C₃H₃O₂ :丙烯酸根） （ 3 ）、[Eu（C₄H₃O₄）₂（H₂O）₇]（C₄H₄O₄）（H₂O）（C₄H₃O₄:单质子化的马来酸,C₄H₄O₄:马来酸）（4）、[Eu₂（C₇H₄O₃）₂（C₇H₅O₃）₂（phen）₃]（H₂O）0.5（C₇H₄O₃:羟基参与配位的邻羟基苯甲酸;C₇H₅O₃:羟基未参与配位的邻羟基苯甲酸;phen:邻菲咯啉）（5）、[La（C₇H₅O₃）₃（phen）（H₂O）]₂（phen）₂（C₇H₅O₃:间羟基苯甲酸;phen:邻菲咯啉）（6）、{[Eu（C₇H₅O₃）（C₇H₄O₃）（phen）₂]（H₂O）}_∞（C₇H₅O₃:羟基未参与配位的间羟基苯甲酸;C₇H₄O₃:羟基参与配位的间羟基苯甲酸; phen:邻菲咯啉）（7）、[Eu（C₇H₆NO₂）₃（phen）]₂（C₇H₆NO₂:间氨基苯甲酸;phen:邻菲咯啉）（8）、[La₂（C₇H₆NO₂）4（NO₃）（H₂O）₂]（C₇H₆NO₂:对氨基苯甲酸）（9）。通过X射线单晶衍射仪对配合物1、2、4、5、6、7、8共七种稀土配合物的单晶结构进行了解析。同时,对上述九种稀土配合物的结构和性能进行了研究表征。2.以合成的聚氨酯丙烯酸酯大分子单体（MUA）为基础,在大单体MUA均聚制备聚合物PUA的过程中,将所合成的稀土配合物引入到MUA的聚合体系中,建立了稀土配合物/大单体原位聚合制备掺杂型稀土聚合物材料的新方法。本文第二章利用该方法分别制备了含稀土配合物1、配合物2的掺杂型稀土聚合物材料RE/PUA,并对材料的结构、性能进行了详细探讨。结果发现,该类掺杂型稀土聚合物材料具有良好的荧光性能,但随着配合物的加入,严重影响了PUA基体材料的透明性,这也是掺杂法制备稀土聚合物材料本身无法回避的缺陷。3.以聚氨酯丙烯酸酯大分子单体（MUA）为基础,将所合成的含活性-C=C官能团的稀土配合物引入到MUA的聚合体系中,通过大单体MUA与配合物中的-C=C双键共聚,建立了稀土配合物—大单体原位共聚合制备键合型稀土聚合物材料的新方法。本文第三章利用该方法分别制备了配合物3、配合物4与大单体MUA共聚的键合型稀土聚合物RE-PUA,并对共聚物材料的结构、性能进行了探讨。结果发现,该类键合型稀土聚合物材料在具有稀土离子的荧光特性的基础上,还具有PUA基体材料良好的透明性（透光率在90%左右）、热稳定性（热分解温度在300℃左右）和力学性能,且材料的荧光强度随稀土配合物含量的增加而提高,在论文实验范围内没有出现荧光猝灭现象,是一类综合性能优良的功能性透明稀土聚合物,有望应用于特殊光学领域。4.以聚氨酯丙烯酸酯大分子单体（MUA）合成技术为基础,将所合成的含活性-OH、-NH2等基团的稀土配合物引入到MUA的合成体系中,合成了含稀土配合物的大分子单体RE-MUA,通过MUA、RE-MUA两类大单体共聚,建立了大单体型稀土配合物—大单体共聚合制备键合型稀土聚合物材料的又一新方法。本文第四、第五章利用该方法分别制备了含配合物5（6、7）、配合物8（9）的键合型稀土聚合物P（RE-UA）,并分别对共聚物材料的结构、性能进行了探讨。结果发现,该类键合型稀土聚合物材料同样具有优良的荧光性能、透明性、热稳定性和力学性能,具有广阔的应用前景;尤其是含配合物8（9）的键合型稀土聚合物还具有良好的抗菌性能,对大肠杆菌具有一定的抑制作用,是一类功能高度集成化的新型稀土功能材料,在未来的新材料领域具有巨大的发展应用潜力。更多还原

【Abstract】 In this dissertation, rare-earth complexes with novel structures were synthesized and introduced into the polymeric system of macromonomers of polyurethane acrylate for achieving a series of transparent rare-earth polymers with excellent photoluminescence performance, based on the study of our research group on the macromonomer of polyurethane acrylate（MUA） and its polymer（PUA）. The structures and properties of such rare-earth polymers have been systematically investigated in detail.1. Nine rare-earth complexes with different ligands, [Tb(C₁₅H₉O₂)₃(C₁₀H₈N₂)]₂ (C₁₅H₉O₂ = anthracence-9-carboxylic and C₁₀H₈N₂ = 2,2-bipyridine) （1）, {[Sm(C₁₆H₈O₄)₂（H₂O）₂](C₇H₁₀N) （H₂O）_1.75}_∞(C₁₆H₈O₄ = anthracene-9,10-dicarboxylic acid and C₇H₁₀N = protonated 2,6- dimethylpyridine) （2）, Eu（C₃H₃O₂）₃ （C₃H₃O₂ = acrylic acid ） （3）, [Eu（C₄H₃O₄）₂（H₂O）7]（C₄H₄O₄）（H₂O） （C₄H₃O₄ = single proeonated maleic acid and C₄H₄O₄ = maleic acid） （4）, [Eu2（C₇H₄O₃）₂（C₇H₅O₃）₂（phen）₃]（H₂O）0.5 （C₇H₄O₃ = salicylic acid coordinated by oxygen aroms from -COOH and -OH, C₇H₅O₃ = salicylic acid coordinated by oxygen aroms from–COOH and phen = 1,10-phenanthroline） （5）, [La（C₇H₅O₃）₃（phen）（H₂O）]₂（phen）₂ （C₇H₅O₃ = m-hydroxybenzoic acid and phen = 1,10-phenanthroline） （6）, {[Eu（C₇H₅O₃）（C₇H₄O₃）（phen）₂] （H₂O）}_∞（C₇H₅O₃ = m-hydroxybenzoic acid coordinated by oxygen aroms from–COOH, C₇H₄O₃ = m-hydroxybenzoic acid coordinated by oxygen aroms from -COOH and–OH and phen = 1,10-phenanthroline） （7）, [Eu（C₇H₆NO₂）₃（phen）]₂ （C₇H₆NO₂ = m-aminobenzoic acid and phen = 1,10-phenanthroline） （8）, [La₂（C₇H₆NO₂）₄（NO₃）（H₂O）₂] （C₇H₆NO₂ = p-aminobenzoic acid） （9）, have been designed and synthesized by hydro-thermal method and conventional solution method, in which complexes 1, 2, 4, 5, 6, 7 and 8 have been structurally analyzed by X-ray single crystal diffractometer. In addition, the structures and the relevant performance of nine rare-earth complexes have been characterized in detail.2. A new method for preparation doping-type rare-earth polymer by rare-earth complex/ macromonomer in situ polymerization on the basis of macromonomer of polyurethane acrylate（MUA）, introducing the synthesized rare-earth complex into the polymeric system of MUA in the process of homopolymerization of MUA for achieving homopolymer （PUA）, has been established. In chapter 2, doping- type rare-earth polymer materials （RE/PUA） containing complex 1 （or 2） have been synthesized by this new method. The structures and properties of RE/PUA have been systematically characterized by infrared spectroscopy （FTIR）, thermogravimetric analysis （TGA）, dynamic mechanical analysis （DMA）, scanning electron microscopy （SEM）, fluorescence spectrophotometer and so on. It is proved that such kinds of doping-type rare-earth polymer materials assume favorable fluorescence. However, the transparency of such PUA matrix mentioned above has been severely affected by the addition of rare-earth complex. As for doping-type rare-earth polymer, the influence of rare-earth on the transparency has been one of the inevitable disadvantages to date.3. A new method for preparation bonding-type rare-earth polymer via rare-earth complex-macromonomer in situ copolymerization based on MUA, introducing the synthesized rare-earth complex containing the reactive group–C=C into the polymeric system of MUA and copolymerizing between the MUA and complex, has been established. In chapter 3, bonding-type rare-earth polymer materials RE-PUA have been prepared through copolymerization of complex 3 （or 4） and the macromonomer of MUA by this method. The characterizations of structures and properties of the RE-PUA show that this kind of bonding-type rare-earth polymer exhibiting not only the fluorescent characteristic of rare-earth ions, but also the excellent transparency （spectral transmittance ⁹0%）, heat stability （the temperature of thermal degradation at 300℃） and mechanical properties, is a novel functional transparent rare earth polymer. Moreover, the results also indicate that the fluorescence intensity of the RE-PUA increase with increasing amount of the relevant complex and without fluorescence concentration quenching within the range of experiment.4. Another new method for preparation bonding-type rare-earth polymer by macromonomer of rare-earth complex-macromonomer copolymerization, on the basis of MUA, introducing the synthesized rare-earth complex containing the reactive group–OH or–NH2 into the synthetical system of MUA and synthesizing the macromonomer of rare-earth complex RE-MUA, copolymerizing between the RE-MUA and MUA, has been investigated and founded. In chapter 4, based on above method, bonding-type rare-earth polymer materials P（RE-UA） containing complex 5 （6 or 7） have been synthesized and characterized, and another P（RE-UA） containing complex 8 （or 9） have been investigated in chapter 5. The results show that this bonding-type rare-earth polymer also have good fluorescence, transparency, heat stability and mechanical properties, similar to that of RE-PUA copolymer reported in chapter 3. Especially, the P（RE-UA） containing complex 8 （or 9） assume favorable antibacterial properties, and have inhibitory effects on colon bacillus.In conclusion, a series of novel rare-earth polymers in this dissertation that exhibit excellent combination properties such as fluorescence, transparency, heat stability and so on were synthesized and structurally characterized. It can be expected, thus, that such rare-earth polymers may find applications in different functional material areas of optical, electrical and magnetic.更多还原