Synthesis, Characterization And Catalytic Performance Of Functionalized Organic Microporous Polymers

In the past decade, organocatalysis has been flourished by many research groups including those of List and MacMillan, and gradually becomes one of the emerging fields in asymmetric catalysis. However, utilization of organocatalysts suffers, still, from high catalyst-loading, expensive cost, and difficulty for recycle use. With respect to this important issue, heterogenization of organocatalysts may offer an effective solution instead. Current strategies for this purpose are mainly focused on the immobilization of organocatalysts onto magnetic nano-materials, inorganic mesoporous materials and polymer resins. On the other hand, polymers of intrinsic microposity (PIMs) and conjugated microporous polymers (CMPs) being developed recently may possess attractive prospects due to their excellent microporous characters, thermal stability, and chemical stability. To the best of our knowledge, however, there have been no reports on the combination of organocatalysts and microporous organic materials. Embedding of organocatalysts into the frameworks of organic microporous materials via covalent bonds may help mass transfer in heterogeneous catalysis, improve the efficiency of catalytic reactions, and avoid the loss of catalytic active centers.Accordingly, the main task of this PhD thesis is to design and synthesize several microporous polymers which are functionalized by hetero-atoms, functional groups, or organocatalysts. Characterization of these functional microporous materials was realized by nitrogen adsorption/desorption isotherms and soild-state NMR techniques. Applications of these organic microporous polymers as heterogeneous catalysts were also exploited.In Chapterâ… , was introduced the research background on microporous materials, and highlighted the development of microporous organic polymers (MOPs). Applications of these organic microporous materials in heterogeneous catalysis, gas storage and separation were, accordingly, reviewed.Chapterâ…¡and Chapterâ…¢describe our attempts in the modification of CMPs by hetero-atoms and functional groups, respectively. In Chapter II, tris-(4-iodo-phenyl)-amine and tris-(4-bromo-phenyl)-borane were applied as precursors to synthesize the functional CMPs containing N or B heteroatoms. Characterization of these CMPs was performed by nitrogen adsorption/desorption isotherms and soild-state NMR techniques. In Chapter III, organic precursors containing-NO2 or-OCH3 groups were utilized to synthesize nitro- and methoxy-functionalized CMPs, respectively.In Chapter IV, asymmetric organic precursors containing the frameworks of organocatalysts, such as L-proline, BINOL, and BINOL-phosphoric acid, were succefully synthesized and further applied in constructing a series of organocatalyst-functionalized CMPs via Sonogashira-Hagihara cross-coupling reactions. The characterization and catalytic applications of these CMPs were conducted accordingly.In Chapter V, an organic nanoporous polymer containing bicovalently-bonded Troger's base in the network constructed by the Sonogashira-Hagihara cross-coupling reaction was synthesized. The structure and microporous properties of the synthesized polymer were further characterized. Moreover, its catalytic activity in the addition reaction of diethylzinc to 4-chlorobenzaldehyde and its ability for hydrogen storage were examined.