Acetals And Ketals Based Microporous Preparation And Properties Of Organic Polymers

The large number of poisonous gas and dust generated along with the extensive use of fossil fuels is threatening human health, and at the same time the emission of large amounts of carbon dioxide and other greenhouse gases is changing the global climate, these all become serious threat of human sustainable development. Therefore, carbon dioxide capture and utilizing new renewable clean energy source, such as hydrogen, are of interest to meet the energy and environmental demands. As a response, big efforts have been devoted to explore suitable materials for carbon dioxide capture or hydrogen storage. Porous organic polymers with the intrinsic properties including large specific surface area, narrow pore size distribution, high chemical and physical stability, and low skeleton density, have exhibited potential applications in energy, environment, and catalysis areas, such as hydron storage, carbon dioxide capture and separation, methane storage and toxic organic solvent vapors adsorption. In this thesis, a series of ketal and acetal-based porous organic polymers were prepared, and their applications towards gas sorption were also investigated.A series of microporous organic polymers with the acetal-linkages were synthesized through the condensation of mutilformyl-containing monomers with pentaerythritol or mannitol with the aid of p-toluene sulfonic acid. This easily-realized archetypal reaction in high yields and the commercially available raw materials, catalysts, and solvents make this condensation display great advantages over other methods for the construction of microporous organic polymers. The FT-IR and solid-state13C NMR spectroscopy confirmed the occurrence of acetal-linkages in the obtained polymers. The highest Brunauer-Emmett-Teller specific surface area for these microporous polymers is approaching980m2g-1. Moreover, their hydrogen and carbon dioxide uptake are also investigated. Generally, we provided a versatile method to prepare porous organic polymers efficiently with promising applications in gas sorption.A series of microporous organic polymers with ketal-linkages were synthesized based on the condensation of aromatic acetyl-containing monomers with pentaerythritol or mannitol. Fourier transform infrared and solid-state13C CP/MAS nuclear magnetic resonance spectroscopy were utilized to confirm the ketal-linkages in the resulting polymers. The morphology can be observed from scanning electron microscopy and transmission electron microscopy images. The highest Brunauer-Emmett-Teller specific surface area for these microporous polymers is approaching950m2g-1, and the highest hydrogen sorption capacity is up to1.96wt%(77K and1.0bar), which is superior to that of most of microporous organic polymers. The facile and cost-effective preparation process and excellent gas sorption properties make this kind of materials become promising candidates for practical applications.In an effort to expand our understanding to the geometric effective of different substitutions towards pore parameters of the obtained porous polymers, we have prepared a series of mutil-substituted tetraphenylethylenes (M1-M4) with different position. Then, a series of microporous organic polymers with ketal-linkages based on the condensation of acetyl tetraphenylethylenes with pentaerythritol or mannitol were synthesized. The highest Brunauer-Emmett-Teller specific surface area for these microporous polymers is approaching614m2g-1.