Synthesis Of Poly(Carbazole)s Via Click Polymerization And Synthesis Andapplication Of Palladium Catalyst

This dissertation mainly focuses on the synthesis and property studies of highmolecular weight poly(carbazole)s via click polymerization and synthesis of newpalladium catalyst. This dissertation consists of seven parts.In the first part, a new kind of conjugated poly(carbazole)s with carbazole as the mainchain was designed and synthesized via click polymerization of3,6-diazido-9-hexylcarbazole and3,6-diethynyl-9-hexyl carbazole. The two monomers with azide andethynyl functional groups were synthesized according to the report literatures with somemodifications which not only considerably improved the yield but also simplified thesynthetic procedures. The chemical structure of these two monomers was fullycharacterized by1H-NMR, FT-IR and microanalysis. Due to incorporation of the longalkyl carbon chain, the monomers have good solubility in most common organicsolvents. Addition polymerization of3,6-diazido-9-hexyl carbazole and3,6-diethynyl-9-hexyl carbazole with Cu(I) as catalyst was investigated in variousconditions. After optimization on the polymerization condition of solvents andtemperature, well-defined conjugated poly(carbazole)s possessing carbazole as thebackbone with extremely high molecular weights were obtained in high yield undermild reaction conditions. The size exclusion chromatography analyses of thesepoly(carbazole)s indicated that the molecular weight can be achieved as high as100000-130000. Moreover, the purity of the synthesized polymers is very high, and nodetectable by-product could be observed on the size exclusion chromatograms. Thethermal and photophysical properties of these novel conjugated poly(carbazole)s werealso studied in solution and in film. Thermal analysis indicate that the polymers haveexcellent thermal stability with Td=359oC and exhibit a glass transition temperature(Tg) of105oC. These poly(carbazole)s exhibited blue-violet light emissions underirradiation with365nm UV light indicated that the triazoles moieties did not impede thefundamental photophysical properties of the carbazole units in the main chains.In the second part, We will synthetic a novel palladium catalyst with a benzene ringthrough a series of reactions of phenyl ring alkynyl ortho to different functional groups.Then polymerization different isonitrile with the newly palladium catalysts. Afterseveral experiments, we can find that this new palladium catalysts with a benzene ringpolymerization easy, good stability, and can be monomer living/controlledpolymerization in isocyanide, The polymer obtained has a high molecular weight and narrow molecular weight distribution.