Study On Synthesis And Characteristics Of Chiral Ionic Porous Organic Polymers

Porous organic polymers?POPs?are a class of highly crosslinked amorphous polymers with nanopores,which have relatively stable pore structure,low relative density,large specific surface area,excellent catalytic performance,and adsorption properties.In recent years,POPs have developed rapidly and attracted interests of many researchers.POPs are categorized into several classes,such as amorphous hyper-crosslinked polymers?HCPs?,polymers of intrinsic microporosity?PIMs?,and conjugated microporous polymers?CMPs?.HCPs can be prepared from a wide range of aromatic monomers with several advantages including the stable structures,easy preparation,high synthetic yield,and low cost,which has important applications in many areas such as gas adsorption and separation,gas storage,micro-pollutant removal,chromatographic separation,heterogeneous catalysis,drug delivery,and sensing.Inthis dissertation,novelionichyper-crosslinked polymers CC-NSA-HCPs@X are designed and synthesized,and their application in the heterogeneous chiral catalysis,dyes and heavy metal ion adsorption,and gas storage are explored.The results demonstrate their extensive and excellent properties.In the third chapter of this thesis,a series of 3,3'-substitued C₂-symmetric chiral quaternary ammonium salt monomers are synthesized firstly.Then,by using dimethoxymethane as cross-linking agent,four kinds of chiral quaternary ammonium based hyper-crosslinked polymers CC-NSA-HCPs@X are prepared by anhydrous ferric chloride catalyzed Friedel-Crafts reaction and anion replacement,and they are characterized in details.Among them,CC-NSA_Naph-HCP@Br polymer exhibites Brunauer-Emmett-Teller?BET?surface area of 788 m² g^-1 with pore volume of 0.57cm³ g^-1.The fourth chapter describes the properties of CC-NSA-HCPs@X in details.Firstly,as novel heterogeneous phase transfer catalysts for asymmetric alkylation reactions,CC-NSA-HCPs@X achieves high yields of 89⁹5%and moderate stereoselectivity of 29⁷1%ee,and they can be recycled and reused.Secondly,dyes and heavy metal ion adsorption experiments demonstrate their high adsorption capacities for anionic dyes?MO,MB?and Cr₂O₇^2-.The maximum adsorption quantities of CC-NSA_Naph-HCP@Br for MB and Cr₂O₇^2-are up to 1009.73 mg g^-1 and744.98 mg g^-1,respectively.Finally,in the gas adsorption study,CC-NSA_Ph-HCP@Br exhibits medium hydrogen storage capacity of 6.16 mg g^-1 at 77 K and 1 bar.Therefore,the novel CC-NSA-HCPs@X process diverse properties,and may have some important potential applications in the heterogeneous chiral catalysis,dyes and heavy metal ion adsorption,and gas storage fields.