Design,Synthesis And Properties Of Porous Organic Polymers

As one of the most important research areas in the 21 st century,porous materials have drawn a lot of attentions in recent years and developed rapidly.These materials have diverse topologies structures and high surface areas.In recent decades,with the improvement of material performance requirements,traditional porous materials including crystalline inorganic frameworks?e.g.,zeolites?and amorphous network structures?e.g.,silicas,activated carbons?have been unable to meet the growing needs of energy and environment.Metal organic frameworks?MOFs?that linked by inorganic units and organic ligands show several advantages,for instance,high surface areas and CO₂ uptakes,but the metal clusters belong to MOFs often result in the materials being less stable to oxygen or moisture so that limit MOFs' practical applications.Porous organic frameworks?POPs?which are constructed by rigid covalent bonds with light elements?C,H,O,N,B,etc.?have been reported with a broad of potential applications in the gas adsorption and separation,catalysis,proton conduction,luminescence and other fields.In this paper,a series of studies on the preparation of new functionalized materials based on POPs and the exploration of new synthetic methods of POPs have been carried out from the perspectives of structural design,synthesis and function applications.The main research contents and results of this paper are as follows:1.We focus on the construction of new IL-functionalized POPs with high surface areas,which provides an easy and low-cost route toward efficient adsorbents for CO₂ using fundamental building blocks.Specifically,a series of IL-functionalized POPs based on p-dichloroxylene?p-DCX?and N-methylimidazole?N-MI?as building blocks were synthesized through Fe Cl₃-catalyzed Friedel-Crafts alkylation reaction and these samples were thoroughly characterized?IR,NMR,CHN,ICP,SEM,TEM,TG,etc.?to understand their structures and properties.The IL-functionalized POPs showed high BET surface areas and CO₂ uptakes.The experimental results indicate the incorporation of ILs moieties can increase the affinity between POPs and CO₂.On the other hand,the as-synthesized IL-functionalized POPs show acid catalytic activity in the synthesis of benzimidazole derivatives from aromatic aldehydes and o-phenylene diamine.2.We focus on the construction of HCPs with high surface areas by using fundamental new building blocks.Herein,a series of organic-inorganic hybrid HCPs based on 1,3,5,7-tetramethyltetraphenylcyclotetrasiloxane [?MePhSiO?₄] as building block was synthesized through Fe Cl₃-catalyzed Friedel-Crafts alkylation reaction by one-step crosslinking approach,formaldehyde dimethyl acetal?FDA?was used as an external crosslinker.These samples were thoroughly characterized?IR,NMR,SEM,TEM,TG,etc.?to understand their structures and properties.We found that the Si-C bonds between the Si and benzene in the?MePhSiO?₄ have been broken during synthesis of HCPs,but the Si-C bonds between Si and-CH3 have no change,the benzene ring separated from building block continue to carry on Friedel-Crafts alkylation reaction with external crosslinker FDA.