Synthesis And Properties Of Carbazole-based Conjugated Porous Polymers

Porous materials have the advantages of high specific surface area,low relative density,light weight,good thermal insulation and permeability,etc.Therefore,more and more researchers pay attention to them.Conjugated porous polymers（CPPs）have adjustable pore properties,high specific surface area,and conjugated system,which makes CPPs show good applications in many fields,such as gas adsorption and storage,catalysis,energy storage,conversion,and chemical sensing materials.At present,the main preparation method for CPPs is chemical synthesis,However,the obtained polymers using chemical synthesis are usually powder,which are insoluble and unprocessable,thus precluding the fabrication of thin films for applications.Moreover,this method requires expensive catalysts and harsh experimental conditions,which limit their applications.With the development of the society,more and more researchers have discovered that electrochemical polymerization is an effective method for the preparation of CPPs films,and the porosity and specific surface area of obtained polymers are comparable to that obtained using chemical synthesis.What’s more,the electrochemical polymerization is high sensitivity,low cost,simplicity,and convenience.The polymer films can be easily obtained,and the thickness,size,and shape of these films can be controlled conveniently.At present,some advances have been made in the study of electrochemical polymerized conjugated porous polymer,and more conjugated porous polymer materials and the new properties of existing materials have yet to be discovered.The main points of this dissertation are summarized as follows:1.TCTA with triphenylamine as the core and carbazole as the peripheral electrochemical polymerization site was selected.The CPP PTCTA films have been successfully synthesized by electrochemical deposition.By controlling the amount of BFEE,we found that PTCTA films obtained from CH₂Cl₂ with 20 vol%BFEE had better electrochemical behavior.The characterizations of the polymer were performed by using FT-IR spectra for structural analysis.Moreover,from the SEM,we observed that different percentages of BFEE are extremely important in the control of the resulting surface morphology.2.BCMF with dimethyl fluorene as the core and carbazole as the peripheral electrochemical polymerization site was selected.The CPP PBCMF films have been successfully synthesized by electrochemical deposition.The PBCMF films obtained from CH₂Cl₂-BFEE mixtures had better electrochemical behavior and better fluorescence than that in pure CH₂Cl₂ solution.FT-IR spectra were used to investigate the structural of polymer films.From the UV–vis and fluorescence spectra of monomer and polymer films,the introduction of BFEE improved the degree of polymerization.However,the introduction of BFEE had no significant effect on the morphology of the polymer and maintained a good porous structure.3.TCPE with tetraphenyl ethylene as the core and carbazole as the peripheral electrochemical polymerization site was selected.We successfully synthesized CPP PTCPE films by electrochemical deposition.With the increase of BFEE content in CH₂Cl₂-BFEE mixed system,the monomer was more easily oxidized,and the electrochemical properties of PTCPE films were improved.It shows that the introduction of BFEE is beneficial to the electrochemical polymerization of TCPE.In addition,FT-IR spectra were used to further determine whether monomers have polymerization reaction and the structure of polymer films.The results showed that these polymers had similar structures and the polymerization of TCPE occurs at 3,6 of carbazole.