Preparation,Characterization And Properties Of Fluorescein-based And Trianiline-based Conjugated Microporous Polymers

In recent years,conjugated microporous polymers?CMPS?,as a material with porous organic framework,have become common functional polymer materials in modern chemistry due to their excellent optical and chemical properties such as fluorescence sensing and high chemical stability.At present,CMPs has been applied to fluorescence sensing nitroaromatic compounds?NACS?,metal ions,electrochemical energy storage devices,catalytic separation,iodine adsorption and other applications.In this graduate thesis,we have prepared four novel conjugated microporous polymers and studied their properties respectively.Two fluorescein containing conjugated microporous polymers?DTF and TTF?were synthesized by the palladium catalyzed Sonogashira–Hagihara polycondensation reactions of tetraiodofluorescein sodium salt?TIFA?with1,4-diethynylbenzene?DEB?or 1,3,5-triethynylbenzene?TEB?.DTF and TTF are porous with the BET surface areas of 705 and 712 m² g^-11 and exhibit high chemical and thermal stabilities.The formation of conjugated polymers with the incorporation of ethynyl groups leads to the fluorescent properties.The fluorescence quenching behaviors of DTF by nitroaromatic analytes in THF suspension are investigated.It is found that the fluorescence of DTF can be effectively quenched by2,4,6-trinitrophenol over 2-nitrophenol?NP?,4-nitrotoluene?NT?,nitrobenzene?NB?,phenol?PhOH?,p-dichlorobenzene?DClB?and 2,4-dinitrotoluene?DNT?with an SV constant of 2.08×10³Lmol^-11 and a detection limit of 7.22×10^-77 mol L^-1(0.165 mgL^-1).In short,the DTF may be a new kind of fluorescence sensing material for detecting TNP.Two nitrogen-rich C₃N₃ triazinyl conjugated microporous polymers?TTDAB and Tm-MTPDAB;?were constructed by Friedel-crak polymerization with2,4,6-trichloro-1,3,5-triazine?TCT?as raw material)?They are derivatives with triphenylamine(1,3,5-tris?diphenylamino?benzene?TDAB?and 1,3,5-tris[?3-methylphenyl?-phenyl]benzene?m-MTDAB?as the core respectively.The purpose of this thesis is to study the effects of triphenylamine derivatives on porosity,iodine adsorption and fluorescence sensing properties.The results show that the properties of TPA can be adjusted by changing the types of TPA.Moreover,despite poor porosity,both TTDAB and Tm-MTDAB have excellent adsorption capacity for iodine(3.13 and 3.04 g g^-1).