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Synthesis Of Salen Mn(Ⅲ)Supported On Zirconium Oligo-polystyrenyl-phosphonate-phosphate And Epoxidation Of Styrene

Posted on:2008-06-10Degree:MasterType:Thesis
Country:ChinaCandidate:D FuFull Text:PDF
GTID:2121360215965915Subject:Organic Chemistry
Abstract/Summary:PDF Full Text Request
The alkene epoxides find important appliction in pharmaceuticals, plastics, perfumes, and pesticide. In this field, the use of Mn(salen) catalysts has received great attention in the last few years, given that they have shown to be useful in the epoxidation of non-functionalized olefins. Despite its interest, this method of epoxidation suffers from some drawbacks from a practical point of view. The high cost of the complex and the lack of recycling methods make it difficult for application of this system on a large scale. The encapsulation of salen complex using ship-in-bottle method and immobilization by ion exchange reaction are given more attention, still little reports are published about the immobilization to organic-inorganic mulriple carriers.The main contents of this thesis as follow:Oligo-styrenyl-phosphonous acid was sythesised by solution polymerization but suspension polymerization, in both H3PO2 was used to modulate the polymerization, because the oil phase and the water phase can't mix completely, so the product are all oligo-polystyrene but not oligo-polystyrenylphosphonate-phosphate acid.Zirconium oligo-chloromethyl-polystyrenylphosphonate-phosphate could be developed from Oligo-styrenyl-phosphonous acid. It's a kind of excellent catalyst support because of its' insolubility in either solvent. Besides, different functional groups can be introduced through kinds of organic reaction.Synthesis of the salen ligand precursor by the relation of utilization an excess of 3,5-ditert-butyl salicaldehyde to 2,4-dihydroxyl benzaldehyde yielded a statistical 9:6:1 ratio of three ligands. Addition of ZCMSPP to the mixture allowed for the selective capture of the hydroxy-terminated li -gands, while the soluble tert-butyl-substituted ligand was washed away from the ZCMSPP bound product. AAS analysis indicated a final loadin g of 1.9 mmol/g of Mn , it's BET surface area is 17m2 /g, and its' SEM shows the reunite form of the catalyst. The supported catalyst was evaluated by epoxidation of styrene, and the effects of oxidation, reaction time, reaction temperature and cocatalysis were also disscusted. The conversion of styrene could be 78 % since the selectivity of oxdistyrene can be 81% in the pH=11.3 buffered solution at 273K. The selectivity of reused catalysis did not decrease for at least 3 runs which indicates that the salen Mn (III) complex is strongly bonded on Zirconium oligo-chloromethyl-polystyrenylphosphonate-phosphateSalen is synthesizd by statistical method and then supported to Zirconium oligo-chloromethyl-polystyrenylphosphonate-phosphate. The epoxidation of styrene indicated that the catalyst is effective, and it's a spread of application of salen Mn.
Keywords/Search Tags:Zirconium oligo-polystyrenylphosphonate-phosphate, Zirconium oligo-chloromethyl-polystyrenylphosphonate-phosphate, supported salen Mn(III), styrene, epoxidation
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