Binaphthalene-based Organic Porous Materials: Preparation,Properties And Application

Porous organic polymers have been studied extensively in a wide range of applications such as gas adsorption and storage, organic electronic materials, heterogeneous catalysis, owing to their high specific surface area, suitable size distribution, flexibility and good thermal stability. The design and synthesis of building blocks is essential to prepare porous organic polymers. The structures of these building blocks play crucial roles in the porosity and gas adsorption of the as-prepared materials. Binaphthalene, as a core structural monomer for designing microporous organic polymers, has been used for the preparation of porous organic polymers. Aromatic spirocyclic compounds based on binaphthalene, with the perpendicular arrangement structure of two planes, are novel core building units to produce contorted polymeric structures, which possess superior morphological stability. In this thesis, a series of research on construction of new materials was carried out, and the characterization and application of new materials were also investigated.The thesis is divided into the following sections:In the introductory chapter, we introduced recent progresses of organic porous polymers, including research background, classification, preparation and characterization of these materials.In chapter2, four building blocks were easily synthesized and well characterized by methods of infrared spectroscopy, nuclear magnetic resonance, mass spectroscopy and so on. The advantages of all reactions have been summarized as follows:firstly, the reaction condition was easily controlled at lower temperature. Secondly, many building blocks were readily obtained in high yield, even higher than the reported literature. Thirdly, pure target products were obtained by recrystallization without other complicated purification.In chapter3, binaphthalene-based porous organic polymers were synthesized efficiently through Suzuki reactions, Sonogashira-Hagihara reactions and oxidative polymerization of thiophenes. The structure, morphology and gas adsorption of the as-prepared materials were well characterized by various types of techniques. According to the obtained nitrogen physisorption isotherms, the Brunauer-Emmett-Teller specific surface areas of these polymers vary from278to859m2g-1. SPOP-7, which has the lower surface area than SPOP-9, possesses1.47wt%hydrogen adsorption capacity at1.0bar and77K, which is competitive with, even higher than lots of porous materials with the same or higher BET specific surface area under the same conditions. Especially, for SPOP-6, the SEM image shows that this polymer consists of relatively uniform monodisperse microspheres with particle sizes about500nm in diameter.