Design,Synthesis And Characterization Of Organic Microporous Polymers Based On Triphenylamine And Azo

Microporous organic polymers?MOPs?has the advantages of large specific surface area,low skeleton density,diverse synthesis methods,acid and alkali resistance and good thermal stability.It has huge application prospect in gas adsorption and separation,and heterogeneous catalysis.Research indicated,the introduction of heteroatom?like N,P,O?into the polymer skeleton can increase the gas adsorption active sites,increase the gas sorption capacities;or by introducing a specific functional group into the skeleton can improve the gas selectivity of MOPs?like CO₂/N₂,CO₂/CH₄?.In the second chapter,two conjugated microporous polymers?TEPS-TPA,TEPM-TPA?were prepared via Sonogashira-Hagihara reaction by using tetra-functional alkyne tetrahedral monomer?TEPS,TEPM?and tri-functional halogen monomer triiodide-triphenylamine?TPA?.TEPS-TPA and TEPM-TPA have high specific surface area,exhibit good gas sorption capacity.The TEPM-TPA has a specific surface area of 1072m²g^-1,the hydrogen uptake capacity is1.4wt%?77K/1.13bar?,the carbon dioxide uptake capacity is 2.41mmolg^-1?273K/1.13bar?and 1.39mmolg^-1?298K/1.13bar?,the methane uptake capacity is0.81mmolg^-1?273K/1.13bar?.The CO₂/N₂ and CO₂/CH₄ selectivity of TEPM-TPA is23.6 and 4.6,respectivelyl.Based on the study of the second chapter,we have explored the effect of functional groups on the properties of the polymers in chapter 3.Two conjugated microporouspolymers?TEPS-Azo,TEPM-Azo?werepreparedvia Sonogashira-Hagihara reaction by using tetra-functional alkyne tetrahedral monomer?TEPS,TEPM?and di-functional halogen monomer 4,4'-diiodazobenzene?Azo?.The specific surface area of TEPM-Azo and TEPS-Azo was 598 m²g^-1 and 564 m²g^-1,respectively,and exhibit excellent CO₂/N₂ gas selectivity of 70.8 and 64.7.In the fourth chapter of this paper,we have synthesized a series of Hyper-crosslinkedMicroporousPolymers?FCTTPASi,FCTTPASi-K600,FCTTPASi-K700,FCTTPASi-K800?,and explored the relationship between the structure and propertites to increase our knowledge of MOPs.The specific surface area of FCTTPASi is 1122m²g^-1,the adsorption capacity of hydrogen is 1.35wt%?77K/1.13bar?,the carbon dioxide capacity is 2.6 mmolg^-1?273 K/1.13 bar?and 1.66mmolg^-1?298 K/1.13 bar?,and the methane adsorption capacity is 0.82 mmolg^-1?273K/1.13 bar?.After the KOH activation of FCTTPASi,the FCTTPASi-K600,FCTTPASi-K700,FCTTPASi-K800 was obtained by carbonization at 600?,700?and 800?,respectively.The FCTPA-K700 exhibits the highest specific surface area and gas uptake capacity,the hydrogen uptake capacity is as high as 2.93wt%?77K/1.13bar?,the carbon dioxide uptake capacity is up to 6.02 mmolg^-1?273K/1.13bar?and 3.33 mmolg^-1?298K/1.13bar?,the methane uptake capacity is2.48 mmolg^-1?273K/1.13bar?.