Preparation Of Novel Porous Organic Polvmers For CO₂ Adsorption And Conversion

Recently,a number of new porous materials have been developed for CO₂ adsorption,separation,and conversion,in order to replace the traditional wet-scrubing methods used in the industrial post-combustion elimination of CO₂.Among them,porous organic polymers?POP_s?with high surface areas,hierarchical porosity,and tunable pore walls,have been paid much attention.More recently,our group reported radical polymerization of vinyl functionalized monomers for the construction of POP_s.In particular,they showed excellent properties in heterogeneous catalysis due to the perfect combination of high ligand concentration and porosity in the materials.Moreover,unlike the metal catalyzed cross coupling reaction used in the synthesis of covalent microporosty materials?CMPs?,the radical polymerization could completely avoid the difficulty for separation of metal catalysts from the solid materials.In this dissertation,we continuously performed the radical polymerization for the construction of POP_s as efficient adsorbents and catalysts for CO₂.From the vinyl functionalized porphyrin monomer,it is successfully obtained the porphyrin based porous organic polymer POP-TPP through a solvothermal radical polymerization.The resulting material have very high surface area and pore volume as well as excellent chemical and thermal stability.After loading metal cations,the resultant polymers of Co/POP-TPP,Zn/POP-TPP,and Mg/POP-TPP not only showed high CO₂ adsorption capacity at 1 atm and room temperature,but also had excellent activities in the cycloaddition of CO₂ and epoxides to form cyclocarbonates under ambient conditions with n-Bu4NBr as co-catalyst.In addition,under the low CO₂ concentration?15%CO₂?,the catalytic activity of the heterogeneous catalyst Co/POP-TPP even outperform those of the homogeneous counterparts,which may contribute to the enrichment of CO₂ in the catalyst.It is worth mentioning that the Co/POP-TPP could recycle for 18 times,giving no obvious decreace in the catalytic activities.Furthermore,it is developed a bipyridine based POP_s?POP-Bpy?from the vinyl functionalized bipyridine monomers.The obtained polymer exhibits high concentration of bipyridine ligands and abundant porosity in the framework,which is favorable for the CO₂ adsorption.As expected,the POP-Bpy gives CO₂ uptake capacity at 2.9 mmol/g at 1 atm and 273 K.After metallation,the resulted M/POP-Bpys showed excellent catalytic activity in the cycloaddition of CO₂ with epoxides to form cyclocarbonates under really mild conditions.The high accessibility of the active Lewis acid sites and the CO₂-philic property of the framework were attributed to their high activities.At last part,it is shown two different kinds of POP_s?POP-Phen and POP-TB?.The POP-Phen was synthesized from the co-polymerization of divinylbenzene and the vinyl functionalized phenanthroline ligands.After metalled with Pd?OAc?2 the obtained Pd/POP-Phen catalyst could perform as an efficient heterogeneous catalyst in the cross coupling reactions of Suzuki,Sonogashira,and Heck reactions.The POP-TB was synthesized from the vinyl functionalized Troger's base v-TB.Because of the basicity of Troger's base in the framework,the POP-TB could efficiently catalyzed the Knoevenagel reactions.