Low Heat Solid-phase Synthesis Of Transition Metal Phosphate And Its Organic Synthesis Activity

Chapter One: Catalytic chemistry is a very important branch of chemistry; catalytic science has significance in national economy. Researches on transition metal phosphates (including natural phosphates and synthetic phosphates) and theirs new developments on organic catalysis were reviewed in this chapter. The reaction principle and the recent developments of catalysis on Knoevenagel Condensation, Michael Addition, and synthesis of butyl acetate were also introduced in this chapter. Research clew and meaning of this thesis were described.Chapter Two: Sodium zinc phosphate, potassium zinc phosphate, sodium hydrogen zinc phosphate, ammonium iron hydrogen phosphate, ammonium iron phosphate hydrate, ammonium zinc phosphate were prepared by solid-state reaction at low heat temperature and characterized by XRD, SEM, TG-DTA, IR. Compared with traditional methods, low heat solid-state synthesis process has many advantages, such as simple, short flow, and environmental protection.Chapter Three: Catalytic activities of sodium zinc phosphate, potassium zinc phosphate on Knoevenagel Condensation, Michael Addition were studied in this chapter. The products were characterized by GC-MS, IR, ~1H-NMR. Experiments show that they have evident catalytic activity in the reaction of benzaldehyde with ethyl cyanoacetate, and benzaldehyde with malonic acid, the yield could reach 81.1 %,62.1 % and 70.0%,75.2% respectively. It is also found that sodium zinc phosphate doped with La has higher catalytic activity. But sodium zinc phosphate, potassium zinc phosphate have no evidence catalytic activity in reaction of ethyl acetoacetate and acrylonitrile. But sodium zinc phosphate supported on KF has catalytic activity, the disubstitued product was obtained, and the yield is 81.8%.Chapter Four: Butyl acetate is an important raw material in organic chemical engineering. The catalytic activity of phosphates prepared via solid-state reaction at low heat temperature on esterification was investigated. The experiment results show that ammonium iron hydrogen phosphate, ammonium iron phosphate hydrate have excellent catalytic activity, esterification rate could reach 94.5%, 97.5% respectively. The two catalysts have many advantages, for example no corrosion to the facilities, high esterification rate, reusable, simplified operation, and less pollution. Uniform design and data mining technology was applied in the experiments.Chapter Five: Thermodynamics researches of sodium hydrogen zinc phosphate, ammonium zinc phosphate were studied in this chapter. According to the Hess Law of thermochemistry, two thermochemical cycles were designed, mensurated necessary data, and calculated their standard molar enthalpies of formation. -3886.179 kJ/mol,-1655.896 kJ/mol are recommended respectively.