Construction And Properties Of Transparent Rare Earth Polymer Based On Macromonomer Of Polyurethane Acrylate

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.