Preparation Of Polystyrene With Ligand On Its Side Chain And Researching On Photoluminescence Character Of Polystyrene-metal Complex

Polymer-metal complexes is a high performance luminescence materials, Thecomplex possesses the excellent photoluminescence and electroluminescence properties,and easy processing characteristics of polymers, Polymer-metal complexes is ainvestigative hotspot in luminescence materials. In this paper, via bond small moleculligands on side chains of polystyrene, two species of polymer-metal complexes wereprepared, and its fluorescence properties were mainly investigated. For polymer-metalcomplexes application provide an important reference in the area of organicphotoelectric materials.Polystyrene （PS） was functionalization-modified with 4-（chloromethyl） benzoicacid （CMBA） as reagent via Friedel-Crafts alkylation action, and benzoic acid （BA）ligand was bonded on the side chains of PS, obtaining the functional macromoleculeBAPS. The chemical structure of BAPS was characterized by FTIR,1H-NMR and UVabsorption spectra. In this work, the functionalization-modification reaction of PS wasmainly investigated. The effects of the main factors on the Friedel-Crafts alkylationaction between CMBA and PS were examined, the reaction mechanism was investigated,and the reaction conditions were optimized. The experimental results show that theFriedel-Crafts alkylation reaction between CMBA and PS can proceed successfully, andthe suitable reaction conditions are as follows: a temperature of 70℃, with N,N-dimethylacetylamide （DMAC） as solvent, and using SnCl4as Lewis catalyst.The binary complex PSBA-Tb（Ⅲ） and PSBA-Eu（Ⅲ） was prepared by thecoordination of Tb（Ⅲ） ion、Eu（Ⅲ） and modified Polystyrene PSBA. The chemicalstructures of the complex were characterized by Fourier Transform Infrared spectroscopy and UV absorption spectra. In this work, the fluorescence emissionproperties of the solution and the film for the complex was mainly investigated. Theexperimental results show that the BA ligands bonded on the side chains of PSBA notonly with double teeth chelating coordination effect, but also can produce significantAntenna effect. The solution and the film of binary complex PSBA-Tb（Ⅲ） possess thestrong characteristic fluorescence emissions spectra of Tb（Ⅲ） ion, and the solution andthe film of binary complex PSBA-Eu（Ⅲ） possess the strong characteristic fluorescenceemissions spectra of Eu（Ⅲ） ion ,the sensitization effect to Tb（Ⅲ） ions of BA ligandswas stronger than to Eu（Ⅲ） ions, or the triple state energy level （T1） of ligands BAmatches well with the resonance level of Tb （Ⅲ） than with Eu （Ⅲ）.The binary complexes PS-（BA）n-Tb（Ⅲ）were prepared by the coordination of Tb（Ⅲ）ion and PSBA .Two kinds of the ternary complex PS-（BA）5-Tb（Ⅲ）-PhenPS-（BA）-Tb（Ⅲ）-（Phen）3were prepared by the coordination of Tb（Ⅲ） ion and PSBAusing PSBA as a macromolecular ligand and phenanthroline （Phen） as a smaller ligand.The chemical structures of the complexes were characterized by Fourier TransformInfrared spectroscopy and UV absorption spectra. In this work, the relationship betweenthe structure and properties including the fluorescence emission properties of thesolutions and the films and the thermal stability for the complexes were mainlyinvestigated. The experimental results show that the apparent saturated coordinationnumber of the binary complex PSBA-Tb（Ⅲ） is 10, which implies that the coordinationof BA to Tb（Ⅲ） reaches saturation and right now the binary complex has a maximumfluorescence as the binary complex has the structure of PS-（BA）5-Tb（Ⅲ）. The ternarycomplex PS-（BA）5-Tb（Ⅲ）-（Phen）1, which is prepared by adding Phen to a solution ofPS-（BA）5-Tb（Ⅲ）, possesses stronger fluorescence emission compared with ternarycomplexes PS-（BA）1-Tb（Ⅲ）-（Phen）3and PS-（BA）1-Tb（Ⅲ）-（Phen）2, which are preparedusing the conventional ratios of reagents5-chloromethyl-8-hydroxyquinoline （CHQ） was first prepared through the reactionHQ and chloromethylation reagent 1,4-bichloromethoxy-butane （BCMB）. Polystyrene （PS） was functionalization-modified with CHQ as reagent via Friedel-Crafts alkylationaction, obtaining the modified Polystyrene HQ-PS. The chemical structures of HQ-PSwas characterized by FTIR and1H-NMR spectra. Polymer-metal complex Mqn-PS wereprepared by the coordination of metal(Al³⁺,Cu²⁺,Zn²⁺) and HQ-PS using HQ-PS as amacromolecular ligand and HQ as a smaller ligand. The chemical structures of thecomplexes were characterized by FTIR and UV spectra. In this work, the fluorescenceemission properties of the solutions and the films for the complexes were mainlyinvestigated. The experimental results show that the Friedel-Crafts alkylation reactionbetween PS and CHQ can proceed successfully. The solution and the films ofPolymer-metal complex Mqn-PS possesses the the strong characteristic fluorescenceemissions spectra, and fluorescence spectrum of films were stronger and red shift thansolution, In comparison with the fluorescence intensity of films and solution, the sizeorder was Znq2–PS>Alq3-PS>Cuq2-PS.