The Synthesis Of Mesoporous Copper Fluoride Hydroxyapatite Catalyst And Its Application In Macromolecular Carbon - Nitrogen Coupling For The Application Of Catalytic Reaction

C-N coupling reaction catalyzed by transition metals with characteristics of high yield, wide range of application, good product separating, milder catalysis conditions and others, has been widely used in organic chemistry research field, such as the systhsis of natural products, biological activity compounds, drug molecules, polymers, LCD, super molecules and some ligand synthesis. Howerever, the traditional catalysts such as Pa, Ni are very toxic, expensive, environmental hazardous and difficult to recycle, which limits its practical application. Here as a new catalyst, Copper fluorine hydroxyapatite (CuFAP) shows great advantage in C-N coupling reaction for its no toxicity, low price, simple synthesis, high stability and easily separated. But as a micropore catalyst, its small pore size and low surface area limits its application in the macromolecular drug synthesis because its low catalytic efficiency, huge dosage use and strict reaction conditions. So researching a suitable method to enlarge the pore size and surface area of CuFAP and improve its catalytic performance on the macromolecular C-N coupling reactions has great significance.In this thesis, two methods were researched to enlarge the pore structure of CuFAP:(1) Synthesize mesoporous hydroxyapatite derectly by using some soft templates such as hexadecyltrimethyl ammonium bromide (CTAB), sodium Dodecyl Sulfonate (SDS), potassium dodecyl phosphate (MAP), and triblock copolymers of F127or P123respectively;(2) Synthesize several kinds of mesoporous materials such as SBA-15, A1SBA-15and CMK-3to load CuFAP. Their catalytic performances on the macromolecular C-N coupling reactions were investigated also. The results are concluded as follows:(1) Using soft templates to synthesize hydroxyapatite, some hydroxyapatite with layered mesoporous structure were gotten, the structure is not stable and easy to collapse at high temperature of550℃(2) The SBA-15shows weak alkali resistance and its structure easily collapse when loading hydroxyapatite; A1SBA-15has stronger alkali resistance ability than SBA-15, and can successfully load differerent amount of hydroxyapatite. But it can’t exist stably in the present of Potassium tert-butoxide; Mesoporous carbon CMK-3can effectively load hydroxyapatite, and the hydroxyapatite nanopaticals are found to be embedded in the wall of CMK-3.(3) The catalytic performances on the target macromolecular C-N coupling reactions of CuFAP and CuFAP/CMK-3with different amount of CuFAP loaded on CMK-3were studied. The results show that CuFAP/CMK-3has a greater catalytic performance than CuFAP. In the same experimental conditions,20%CuFAP/CMK-3shows the best catalytic activity. This is probably due to its more loading of CuFAP and higher surface area. The5%CuFAP/CMK-3shows the best catalytic efficiency of unit mass for its minimum partical size, highest surface area, and highest content of Cu2+in the unit mass of CuFAP loaded on CMK-3to expose most catalytic positions than others.(4) The regeneration experiments of CuFAP/CMK-3show that when the CuFAP/CMK-3after the catalytic reaction was exchanged with Cu2+again, its catalytic efficiency reduced, this might because the apitite nanopaticals grew up together on the CMK-3and the catalytic activity positions on CuFAP/CMK-3reduced.