Synthesis, Characterization And Properties Of Novel Conjugated Microporous Polymers

In recent years,many countries have been plagued by energy shortage and environmental pollution,that makes people seek contermeasures actively.Traditional fossil fuels?coal,oil and natural gas?can not be reused and will pollute the environment seriously,and one of these pollution is air pollution from the excessive CO₂ emission.In order to solve this problem,researchers have developed a series of functional materials with properties of CO₂ adsorption and storage.These materials can reduce the CO₂content in the atmosphere effectively.Microporous organic polymers?MOPs?are widely used in the field of gas adsorption due to the facile preparation strategy,the high physicochemical and thermal stability,the high surface area,and the outstanding CO₂sorption performances they have.According to their molecular structure,MOPs can be dividedintofourcategories:polymersofintrinsicmicroporosity?PIMs?,hypercrosslinked porous polymers?HCPs?,conjugated microporous polymers?CMPs?,and covalent organic frameworks?COFs?.In this thesis,we designed a series of monomers with different structures and prepared a series of CMPs through Sonogashira-Hagihara coupling reaction and/or homocoupling reaction.Then we characterize these polymer materials and studied their gas adsorption properties.The details were as following:1.We synthesized three phosphine-containing CMPs from triphenylphosphine oxide?TBPPO?with different triangular arylethynylene linkers?TEPA,TEPM and TEPP? via Sonogashira-Hagihara coupling reaction.TBPPO-TEPA exhibit moderate Brunauer-Emmett-Teller?BET?surface area up to 742 m²·g^-1 and a high CO₂ uptakes of 2.61 mmol·g^-1?273 K/1.13 bar?.This polymer shows CO₂/N₂ selectivity ratios of 60.2 and CO₂/CH₄ selectivity ratios of 5.7.The isosteric heats of adsorption(Q_st)of these three polymers are in the range from 28.9-31.5 kJ·mol^-1.Given the high CO₂ uptake and CO₂ over N₂ selectivity,these CMPs with P=O polar group might have great potential in the area of gas adsorption and storage.2.We synthesized three phosphine-containing CMPs from triphenylphosphine sulfide ?TBPPS?with different triangular arylethynylene linkers?TEPA,TEPM and TEPP?via Sonogashira-Hagihara coupling reaction.TBPPS-TEPA exhibit moderate Brunauer-Emmett-Teller?BET?surface area up to 883 m²·g^-1 and a high CO₂ uptakes of 2.48 mmol·g^-1?273 K/1.13 bar?.This polymer shows CO₂/N₂ selectivity ratios of 55.3 and CO₂/CH₄ selectivity ratios of 5.0.The isosteric heats of adsorption(Q_st)of these three polymers are in the range from 26.1-31.0 kJ·mol^-1.Given the high CO₂ uptake and CO₂ over N₂ selectivity,these CMPs with P=S polar group might have great potential in the area of gas adsorption and storage.3.We synthesized three homo-coupled polymer networks based on triphenylamine,methyltriphenylsilaneandtetraphenylsilane.TEPA-MOPexhibitmoderate Brunauer-Emmett-Teller?BET?surface area up to 715 m²·g^-1 and CO₂ uptakes of 1.59 mmol·g^-1?273 K/1.13 bar?.This polymer shows a high CO₂/N₂ selectivity ratios of 73.6 and CO₂/CH₄ selectivity ratios of 5.8.The isosteric heats of adsorption(Q_st) of these three polymers are in the range from 25.6-27.8 kJ·mol^-1.Given the high CO₂ over N₂ selectivity,these homo-coupled CMPs with alkynyl-bridge might have great potential in the area of gas adsorption and storage.