Prepapration And Application Of Helical Polyaniline Supported Catalysts

Polyaniline （PAN） is a classical conducting polymer with desirable electrons transferperformance, special doping-dedoping mechanism, adjustable redox property and insoluble inwater and most organic solvents. It was successfully employed as a catalyst support in avariety of organic transformations, such as photocatalysis, aldol oxidation, carbonyl addition,Suzaku, Heck and oxidation reaction of alkenes. In this thesis, a supported polymer catalystwas prepared and applied to the oxidation of styrene. In addition, a new chiral Schiffbase-aniline and camphor sulfonamides-aniline was studied.A study of polyaniline and poly m-phenylenediamine （PmPD） manganese catalysts hasbeen presented. The catalysts were prepared by supporting MnSO4, Mn（OAc）2andMnCl（Salen） on the polymers. The supported catalysts were characterized and applied to theoxidation of styrene. The results indicated that the catalytic activity was probably related tosupporters, sources of manganese and metal concentration. The supported catalysts turned outto be efficient and selective for the oxidation. PmPD supported Mn（OAc）2catalysts showedthe highest catalytic activity. Under the certain condition, the conversion of styrene and theselectivity to benzaldehyde were98.5%and97.6%, respectively.A cobalt-functionalized helical polymer was prepared by supporting Co（OAc）₂respectively on the helical poly m-phenylenediamine （PmPD） and polyaniline （PAN）, dopedwith （1R）-camphorsulfonic acid （R-CSA）. The Cobalt-supported helical polymer catalystswere characterized applied to the asymmetric ammonia addition of fumaric acid and theepoxidation of styrene for evaluated the catalytic activity. Results informed that the helicalcolbalt/polymer catalyst was moderate and efficient for the asparticacid synthesis under hightemperature, the productivity raised from70%to91-95%, but showed little enantiomericexcess value. In the asymmetric epoxidation of styrene under room temperature, the catalystslead toenantiomeric excess of phenyloxirane （9.6%-11.7%）. It might be ascribed to theinduction of catalyst’s helical structure.Beyond that, a study of new chiral aniline monomer and its polymerization wasundertook in this thesis. Chiral Schiff base-aniline and camphor sulfonamides-aniline wasprepared. Each was synthesized by conventional and solventless method respectively. Thephysicochemical properties and spectrograms of intermediates and products showed that it isfeasible to prepared chiral monomer and polymer in new ways. Oxidized polymerization wasused to prepare the monomer directly without chiral inducer. CD spectra also showed theexistence of chiral structures.