Of Tb <sup> 3 + </ Sup> Complexes And Their Synthesis And Properties Of Polymer Fluorescent Material

In this paper, the formulated detailed technical route to enhance the fluorescence intensity of rare earth organic compounds and the optimizing preparation methods of rare earth luminescent polymeric material. The main researching routes are as follows: (1) Six kinds of terbium binary and ternary organic complexes were synthesized, and a series of heterogenous rare earth doped terbium complexes were synthesized as well. The performance and structure of the complexes were studied. The photoluminescence property of the complexes was tested. The influence on the fluorescence intensity of heterogenous rare earth ions was investigated. The enhancing mechanism of the rare earth doped complexes was discussed in this paper. (2) The bonding-type Tb³⁺ fluorescent polymeric material with regular shapes and excellent transparency was synthesized by bulk free radical copolymerization. The complexes which have polymerization activity and good luminescent property were co-polymerized with the co-monomers. The relationship between the material properties and the complexes contents was studied. (3) By blending process, the synthesized terbium organic complexes were blended with the common polymer materials by mechanical blending technics which was usually used in polymer process; the Tb³⁺ blending-type fluorescent polymeric material was prepared. The influence on the composite material of the complexes was tested. The mainly study works are as follows:1. The Study on synthesis and properties of terbium complexesTerbia (Tb4O7) was used as raw material and the cheap monocarboxylic acid was used as feminine ligand, 1, 10-phenanthroline (phen) was used as synergism ligand, the binary terbium complexes and ternary terbium complexes were synthesized in water-ethanol medium. Elemental analysis, infrared spectrum(IR) ultraviolet absorption spectrum(UV) and single crystal X-ray diffraction were used in analysising the components and structures of the complexes. X-ray powder diffraction (XRD) and analysis (STA), the photoluminescences performance was measured by fluorescence spectrometer at different states and environments, and the fluorescence intensity were compared among the complexes.A series of terbium-benzoic acid complexes doped with different heterogenous rare earth ions were synthesized by coprecipitation. The structures of the complexes was analysised and surmised, the photoluminescences performance of all the complexes was measured, the influence on the fluorescence intensity of the complexes with the sorts and the proportions of doped rare earth ions was studied, the properties of the doped ions may generate"the effect of fluorescence sensitized"were summarized, and the mechanism of the fluorescence sensitize was investigated.2. The Study on preparation and properties of fluorescent polymeric material containing Tb³⁺Moulding technique was used in the bulk free radical copolymerization of the complexes and the co-monomer. As a result, Tb³⁺ ion was successfully introduced into the polymeric material. A series of transparent Tb(MAA)3phen-MAA-St copolymer sheets with different contents of terbium complexes were prepared. The configuration of the terbium complexes existed in the copolymers was characterized by IR,UV,XRD and SEM. The influence on the thermal properties and mechanical properties of the copolymer with different content of the complexes was investigated. The relationship between the fluorescence intensity of the copolymer sheets and the mass concentration of the complexes was discussed.Tow kinds of blending-type rare earth fluorescent polymeric material were prepared by traditional melt process. The blending behavior of the complexes in different polymeric matrix was discussed. The influence on the mechanical properties of the polymeric matrix with the different contents of the complexes was studied. The fluorescence intensity of the composites was tested. And the fluorescence performance of the composites was analyzed.The results showed that all the complexes and the rare earth fluorescent polymeric materials show the characteristics transition fluorescence emission of Tb³⁺. The chemical compositions of the binary and ternary organic complexes were TbL3 and TbL3phen (L means the carboxylic acid). The two carboxylate oxygen atoms of the monocarboxylic acid were coordinated with the RE ion, and the two nitrogen atoms of phen was coordinated with the RE ion. The introduced 1, 10-phen could enhance fluorescence intensity of the corresponding binary complexes greatly. The crystal property of the ternary complex was batter than the binary complex. But the thermal stability of the ternary complexes was reduced. The doping ions lead to sensitization showed in the testing of the luminescence properties of the complexes. The Gd³⁺, Y³⁺ ions sensitized fluorescence of benzoate terbium was better than La³⁺ ion. The rare earth complexes were chemical bonding in the copolymer. And the rare earth ions were well distributed and difficult to gather with each other in the copolymers. The "concentration quenching phenomenon" of fluorescence intensity did not appear in copolymer. The copolymer sheets have good transparent performance and mechanical properties. Just a little amount of complexes lead to the better fluorescence properties of the materials in the blending-type rare earth fluorescent polymeric materials,. In rigid polymer, the composite shows the toughening effect with a little amount of the complexes. But the two kinds of the composites showed varying degrees of "concentration quenching phenomenon".The significance of the research works in this paper is aimed to the secondary and advanced Tb³⁺ products development, study the luminescent properties of the products, and discover the methods to enhance the fluorescence intensity of them. Prepare the rare earth fluorescent functional polymeric materials by physics or chemistry methods, study the properties of materials in order to obtain high-performance rare earth functional polymeric materials which have potential application by simple synthesize methods or groovy processing procedures.