Synthesis And Luminescent Properties Of Novel Rare Earth Complexes Containing Macromolecular Ligand

Polymer rare earth complexes possess excellent luminescent properties and good processability. The study on preparation and properties of these materials is significantly important for both academic research and practical applications in a variety of fields such as light-emitting display, information and communication, solar energy conversion, and so on. In this thesis, two series of novel polymer rare earth complexes were prepared via coordination reaction between rare earth ion and macromolecular ligand containing aromatic carboxylic acid. The luminescent properties of these polymer rare earth complexes were also discussed. Furthermore, the fluorescent nanofibers of these complexes were successfully prepared by electrospinning. The main works of the present thesis are listed as follows:A series of PMMA-HEA copolymers were prepared by free radical polymerization of methyl methacrylate(MMA) and hydroxyethyl acrylate(HEA). The resulted polymers were characterized by a combination of contact angle, IR, DSC, TGA and GPC. The results indicated that the polymers were random copolymers and their hydrophilic property increased with the increase of HEA content. The copolymers reacted with trimellitic anhydride, where trimellitic anhydride was bonded on the side chain of the polymers, resulting the macromolecular ligand. Then, a series of novel polymer rare earth complexes were prepared via coordination reaction between the macromolecular ligand and rare earth ion(Eu3+, Tb3+), yielding PMMA/RE luminescent materials. PMMA/RE/Phen luminescent materials were also prepared using l, 10-Phenanthroline(Phen) as synergistic ligand. These luminescent materials were characterized by GPC, fluorescence spectra and ICP-AES. The results showed that the rare earth ions coordinated with polymer successfully and the luminescence intensity increased with rare earth ions content.The nanofibers of these complexes were prepared successfully by electrospinning. The Average diameter of PMMA/Eu/Phen nanofiber is 150 nm, and the diameter distribution is in the range of 100-350 nm. PMMA/Tb/Phen nanofiber surface is smooth, average diameter is 160 nm, and the diameter distribution is in the range of 100-330 nm.A series of PS-HEA random copolymers were prepared by free radical polymerization of styrene(St) and HEA. The PS-HEA copolymers reacted with trimellitic anhydride, providing macromolecular ligand containing aromatic carboxylic acid on the side chain. Using them as macromolecular ligand and phen as synergistic ligand, PS/RE/Phen luminescent materials were prepared. The GPC and fluorescence spectra results showed that the rare earth ions successfully coordinated with polymer and the luminescence intensity increase with the rare earth ions content. PS/RE/Phen nanofibers were also prepared by electrospinning technology. The SEM results showed that PS/Eu/Phen nanofibers with the diameter in the range of 80-130 nm are arranged randomly. PS/Tb/Phen nanofiber surface is smooth, their average diameter is 140 nm, and the diameter distribution is in the range of 80-200 nm.