The Preparation And Properties Of N-containing Conjugated Microporous Polymers

In this paper, seven types of N-containing conjugated microporous polymers(CMPs) were synthesized by three heterocycle monomers and two ethynyl benzene monomers via Pd(0)/Cu(I)-catalyzed Sonogashira-Hagihara crosscoupling reaction in diverse solvents. We investigated morphology and adsorption property for different metal ions, dyes and iodine, which were infuenced by diverse ethynyl benzene monomers, 2,5-dibromopyrazine and its isomeric monomer or various solvents in three chapters, respectively.The chemical composition, morphology, thermal stability, porosity and gas storage capacity of novel N-containing CMPs were investigated by Fourier transform infrared spectroscopy(FTIR), 13 C solid-state NMR spectra, scanning electron microscope(SEM), thermal gravimetric analyzer(TGA) and Brunauer-Emmett-Teller(BET) analysis. FTIR and 13 C solid-state NMR spectra show that the resulting CMPs are composed of benzene, alkynyl and N-containing heterocycle. The SEM images of above mentioned CMPs exhibit diverse morphology, such as sphere structures, 3D network structures and layered structures. TGA show that all the CMPs exhibit good thermal stability and PCMP-1 have best thermal stability. BET analysis of seven types of CMPs show diverse porosity. PCMP-1 exhibits the highest BET surface areas of1136 m2 g-1. The CO2 gas sorption of some CMPs samples show the CO2 uptake is20.5-109.0 mg g-1. The adsorption of Zn(II)、Cr(VI)、 Ni(II) and Cu(II) show that the adsorption capacity of PCMP-2 contained 1,4-diethynylbenzene are better than PCMP-1 contained 1,3,5-triethynylbenzene. The CMPs contained2,5-dibromopyrazine or its isomeric pyridazine monomer exhibit different adsorption capacity for metal ions. The dyes adsorption tests show that the adsorption capacity for methyl orange and rhodamine B of BQCMP-2 contained 1,4-diethynylbenzene are better than BQCMP-1 contained 1,3,5-triethynylbenzene. The resulting CMPs(BQCMP-1, BQCMP-3, BQCMP-4) in different solvents exhibit diverse adsorption capacity for methyl orange. The I2 capture of seven CMP samples is 0.89-2.32 g g-1.In this paper, we synthesized novel N-containing CMPs by designing chemical constitution of monomers. Our study may provide a new guidance for some specific fields. For instance, the incorporation of metal ions and heteroatoms into CMPs can obviously enhance the catalytic activity and the interaction between CO2 and adsorbents.