Synthesis And Catalytic Epoxidation Reactions Of Mn(Salen) Axially Immobilized On Zirconium Poly(Styrene-isopropenyl-phosphonate)-phosphate

In the thesis, heterogenized Mn(salen) catalyst was prepared by the combination method of be fixed on zirconium poly(styrene-isopropenylphosphonate)-phosphate and its catalytic activities on epoxidation of alkenes were investigated.Linear styrene-isopropenyl phosphonic acid copolymer is synthesized by free radical solution reaction with Isopropenyl phosphonic acid (IPPA) which posses double bond and styene for the first time. The IPPA units were distributed as single unit embedded among the polystyrene segments, as—(St)_l-IPPA-(St)_m-IPPA-(St)_n—and which is characterized by ¹H NMR, ³¹P NMR, IR and Acid-base Titration. The affection of solution, amount of initiator and ratio of monomer for the content of phosphonic acid was investigated. The phosphonic acid copolymer with different content of phosphonic acid, molecular weight and different chemical and physic properties was synthesized.The corresponding zirconium poly(styrene-isopropenylphosphonate)-phosphate (ZPS-IPPA), a new kind of organic-inorganic hybrid catalyst supports which is insoluble both in aqueous,organic solvent and own good stability and easiness of being functionalized were also prepared for the first time. The styrene-isopropenyl-phosphonic acid copolymer and ZPS-IPPA were characterized by IR, and the later were also characterized by surface area, TG. The possible structure model of the prepared ZPS-IPPA were deduced and proposed based on experiments. The chloromethyl-ZSP-IPPA with high content of chloride was made by the reaction of chloro(methoxy)methane and ZSP-IPPA. The final scheme of ZSP-IPPA chloromethylation was found by rhombic. The amination of ZSP-IPPA was made successfully by the reaction of the chloromethylation product with ethylenediamineMn(salen) complex was obtained by the coordination of Mn(0Ac)2 with the ligand which was synthesized by the reaction of 3,5-di-tert-butyl-salicyaldehyde with ethylenediamine. The catalyst and its precursor were characterized by FI-IR, 1H NMR respectively. The catalyst of Mn(salen) axially immobilized onto ZSP-IPPA was obtained by the reaction between amination product of ZSP-IPPA andMn(salen).The factor, such as useage of catalyt and co-catalyst, of epoxidation of cyclohexene and styrene was investigated by the catalysis of Mn(salen) axially immobilized onto ZSP-IPPA with NaClO as oxidant. The results of experiments show that the solidborne multi-phase catalyst has better selectivity and reusable. Although the activety was decreased, the conversion could reach 33% with increasing the amount of catalyst...