Synthesis And Properties Of Rigid Ionic Porous Organic Polymers Based On Zincke Reaction

Ionic porous organic polymers（iPOPs）are a class of new porous organic polymers with electrical charges.Their physical and chemical properties,functional groups and active sites can be easily adjusted by counter ion exchange.Therefore,it has been more and more widely used in the fields of gas storage and separation,water purification,heterogeneous catalysis,energy conversion and storage.Especially for rigid iPOPs,due to the existence of rigid conjugated structures,it also shows good application prospects in the field of photocatalysis.The Zincke reaction is a new method for the efficient synthesis of rigid iPOPs developed in recent years,but most of the research are have been limited to Zincke monomers with viologen structure and subsequent porous polymers.There are still few reports of new Zincke monomers and rigid iPOPs with more extended conjugation.Therefore,this paper designed and synthesized new Zincke monomers with different conjugated bridge structures,and reacted with triazine triamine compounds through Zincke reaction to construct a series of new rigid iPOPs,and further studied their dyes adsorption properties and the performance of photocatalytic synthesis.The specific research results are as follows:1.Zincke monomers with different conjugation degree were designed and synthesized,and then rigid iPOPs-1 and iPOPs-2 with adjustable pore size and specific surface area were successfully synthesized through Zincke reaction.The chemical structure,pore size distribution,morphology and stability of the two polymer materials were characterized by infrared spectroscopy,solid-state nuclear magnetic ¹³C CP/MAS NMR,XRD,TGA,FE-SEM,nitrogen adsorption and CO₂ adsorption capacity.It was found that by changing the size of the conjugated bridge,the pore size and specific surface area could indeed be adjusted.The adsorption performance of the two polymers on the model dyes was studied.The results showed that:Both iPOPs have good adsorption properties for methyl orange（MO）with small molecular size,however,iPOPs-1 cannot adsorb methyl blue（MB）with a larger molecular size;iPOPs-2 can completely adsorb MO and MB.This result further confirmed the sieving effect of the pore size.2.Designed and synthesized a Zincke monomer with an anthracene ring structure,and then successfully synthesized a new donor-acceptor（DA）type iPOPs through the Zincke reaction,named AN-POP-1.The chemical structure,pore size distribution,morphology and stability of polymer material was characterized by infrared spectroscopy,solid nuclear magnetic ¹³C CP/MAS NMR,XRD,TGA,FE-SEM and nitrogen adsorption,and was analyzed by solid ultraviolet and electrochemical tests its photoelectric properties.It was found that by introducing D-A structure into the material skeleton,the porous polymer has good photoelectric properties.Furthermore,using benzylamine oxidative coupling reaction as a model reaction,its visible light photocatalytic activity was investigated.The results showed that as a new type of heterogeneous photocatalyst,it has good photocatalytic performance for benzylamine oxidative coupling reaction,and has excellent circulation and stability.