Terbium, Samarium Ternary Complexes Of Fluorescent Polymer Ink Resin Of The Synthesis And Study

Rare earth elements possess luminescent, electric and magnetic properties due to their particular electron structure, and these properties can also be changed, modified and strengthened through interacting them with the ligands and can be used to manufacture many hi-tech materials, so they are called the resources of new materials.Fluorescence counter-imitated printing ink is a kind of special printing ink producing visible light under UV, so it can be used as counter-imitated material, and print various counter-imitated brands, securities, light identified system, bar code label, mail and RMB's invisible signs. Chemosynthesis rare earth complexes possess good luminescent properties and consistency; it is possible to develop new counter-imitated materials to apply them to the fluorescence printing ink resins.The luminescence complexes of terbium and samarium in this paper related to ones that can absorb radiant energy and can produce photoluminescence. The first ligands rated to these complexes principally are inexpensive benzoic acid and its derivatives, such asβ- diketones, which have good luminescent performance. Luminescent intensity of thecomplexes is improved and the cost is lowered by doping inexpensive no-fluorescent inert ions. Fluorescent agents with good disperse were prepared by Sol-Gel method, we study the synergetic effects of second ligands and luminescence enhancement effects of doping ions,and improve the luminescence of complexes step by step. Our main works are as followings:1.The binary complexes of terbium and samarium with benzoic acid and its derivatives(benzoic acid,p-methylbenzoic acid,p-aminobenzoic acid,acetylacetone, salicylic acid,sulfosalicylic acid) were synthesized and their fluorescence properties compared. The IR spectra showed that the IR spectra of complexes are different from those of free ligands. The fluorescence properties of them were investigated by using luminescence spectroscopy, the results showed that all the six complexes of terbium exhibited excellent fluorescence intensity, and the complexes of terbium with sulfosalicylic acid had thestrongest fluorescence intensity. To samarium ion,their fluorescence properties of its complexes with these ligands were inferior to corresponding terbium complexes,only three complexes show better luminescence,they were Sm-benzoic acid,Sm-p-methylbenzoic acid, Sm- acetylacetone acid, while Sm-sulfosalicylic acid, Sm-p-aminobenzoic acid, Sm-salicylic acid, exhibited the ligands'wide band emission.2. In the base of the step1, The ternary complexes of terbium and samarium were synthesized in the introduction of the second ligands, 1,10-phenanthroline. Their molecular compositions and structures were characterized by means of elemental analysis, EDTA titrimetric method, FT-IR and UV spectroscopies; their thermal properties were studied by thermal analysis instrument; their luminescent properties were investigated by means of fluorescence instrument. The main results are as follows: All the spectra of terbium ternary complexes are similar, and emit the characteristic green fluorescence of 5D4—7F5,5D4—7F6,5D4—7F4 of terbium ion. Among the terbium complexes of aromatic carboxylic acid and phenanthroline, the ability order that the ligands transfer energy to the central terbium was p-methylbenzoic acid > sulfosalicylic acid > benzoic acid > acetylacetone acid > salicylic acid > p-aminobenzoic acid. Among the terbium ternary fluorescence complexes that we had synthesized, Tb(PMBA)2(Phen)·3H2O has the best fluorescence and thermo stability properties. All the spectra of samarium ternary complexes are similar, and emit the characteristic red fluorescence of 5D0—7F1,5D0—7F2,5D0—7F3 f samarium ion.3. Twelve fluorescence printing ink resins had been synthesized by mixing the terbium and samarium ternary fluorescence complexes into the polymers. Their luminescent properties were investigated by means of fluorescence instrument; the results indicate that all the fluorescence printing ink resin and polymers produce the similar green and red characteristic fluorescence as terbium and samarium ternary complexes.