The Synthesis And Adsorption Study Of Pyrene-cored Porous Organic Polymers

Recently covalence-linked porous organic polymers(POPs)have been widely applied in the field of the gas storage and separation,heterogeneous catalysis,light harvesting and so on due to their large surface area,fine-tuned porosity,low density,high thermal stability and flexible processability of organic building blocks.In the area of gas storage and gas seperation,POPs?s uptaking and sequestrating has appealed a great amount of interest.This has attributed to the excessive consumption of fossil-fuel,which results a strong increase in the release of greenhouse gases especially carbon dioxide on the human activity.In addition,the technology of storing the clean energy such as CH4 and H2 has also become a hot topic,which can provide clean power for the sustainable development of our society.Thus,it will display substaintial values that design and synthesis new porous materials which can be used for practical applications.In this thesis,we report three series porous organic polymers via different organic-based synthesis strategies and confirmed their features of structure,thermal stability,morphology and so on.Besides,we tested their CO2 storage and sequestration abilities as well.The following is the major content of this thesis.(1)The 1,3,6,8-tetrabromopyrene was used as start raw material to react with2-thienylboronic acid and 3-thienylboronic acid via the Suzuki cross-coupling reaction to obtain the comonomers L1 and L2,respectively.Then,the covalent organic polymers CK-COP-1 and CK-COP-2 were synthesized by the oxidative polymerization of the thiophene containing monomers,L1 or L2,with FeCl3.In this series,L1 and L2 were two isomeric thiophene substituted pyrenes.However,for the L1 and L2,the position of the thiophene attached on the pyrene untis changes the reactive sites for the oxidative polymerization,which control the crosslinking degree,the poroe size distribution,the thermal stability,the gas storage and sequestration ability of the final COPs.For example,the CO2 storage of the CK-COP-1 and CK-COP-2 are 2.85% and 9.73%,at 273 K and 1 bar,respectively.Hence,we speculate that when design the new porous adsorbents the crosslinking degree of the building blocks is the same crucial factor with the special organic functional group.(2)The 1,3,6,8-tetrakis(p-formalphenyl)pyrene was used as the start raw material to react with phloroglucinol and 1,5-dihydroxynaphthalene via phenolic resin-inspired chemistry to afford microporous polymeric organic frameworks(POFs)ZLY-POF-1 and ZLY-POF-2,with hydrochloric acid.Although in the both the ZLY-POF-1 and ZLY-POF-2the pyrene was used as the core,their coupling model and pore size distribution exhibited large differences,which were attributed to the numbers of hydroxide radical and rigid degree of plane between the phloroglucinol and 1,5-dihydroxynaphthalene.This has also caused the diffetent CO2 storage and sequestration abilities of the two ZLY-POFs(ZLY-POF-1,11.26%;ZLY-POF-2,7.76%;273 K,1 bar).(3)The conjugated microporous polymers(CMPs)LKK-CMP was synthesized via the oxidative dimerization of terminal alkynes on the planar tetrafunctional alkyne(1,3,6,8-tetraethynylpyrene),with the Pd(?)-Cu(?)catalysts.LKK-CMP exhibits high thermal stability and microporous characteristics.It also features alternative arrays of pyrene and alkyne groups,which endowed itself with high conjugated skeleton.The rich electrons of the building block can translate through all the skeleton of LKK-CMP,which can offer a great possibility of weak intereaction between the non-polar guest gas(CO2)and low-polar polymers.In addition,the weak interactions are beneficial to the cost-and energy-effective regeration of the porous adsorbent LKK-CMP.LKK-CMP can absorb CO2 9.78% at 273 K,up to 1 bar and exhibit high CO2/CH4(6.8)and CO2/N2(52.8)selectivities.