The Preparation And Study Of Novel Luminescent Polymer Materials Containing Thiophene Or Carbazile Units

This thesis describes some research of light-emitting polymer materials containing thiophene or carbazole units, the main contents are as follows.(1) Poly(3-hexylthiophene)-b-poly(n-decyl-iso-cyanobenzoate) was synthesized in a single pot via the addition of 2-bromo-3-hexyl-5-chloro-magnesiothiophene followed by n-decyl 4-isocyanobenzoate to a solution of Ni(1,3-bis(diphenyl -phosphino)propane)Cl2. The respective mechanistically distinct polymerizations proceeded in a controlled fashion and afforded well-defined block copolymers with tunable molecular weights and compositions. Certain copolymers exhibited solid state microphase separation.(2) Coupling of ethynyl terminated poly(3-hexylthiophene) with azide terminated poly(γ-benzyl L-glutamate) afforded the respective block copolymer in good yield and high purity; this material was found to self assemble into hierarchal structures in solution and in the solid state.(3) The synthesis and characterization of a family of novel main chain carbazole-containing polymers that were prepared using copper-catalyzed azide-alkyne cycloaddition (CuAAC) chemistry is described. The reaction was performed under mild conditions using a highly stable catalyst, which afforded soluble and readily isolable polymeric products. High thermal stabilities (>270℃) and high quantum efficiencies highlight the potential of using these polymers in organic light emitting diodes (OLEDs) or other similar emissive materials, particularly where efficient blue emission is of value (λem= 448 nm). In addition, the CuAAC approach described offers significant practical advantages over other synthetic methods used to prepare main chain carbazole-containing polymers, especially with regard to the lack of need for rigorously inert conditions and the absence of byproducts generated during preparation of the polymer. (4) Polycondensation of 9-(4-aminobenzene)-carbazole with 4,4'-difluorobenzoph -enone afforded 4-(9-carbazole)-benzene-poly(amido aryl ketone) (PAK-Cz). Similarly, a series of novel copolymers containing poly(ether ether ketone)s with pendant carbazoles (PEEK-Cz) and poly(aryl ether ketone) containing pendant carbazoles (PAEK-Cz) were synthesized from 9-(4-aminobenzene)-carbazole,4,4'-difluorobenzophenone and 4,4'-biphenol (BP) or 4,4'-isopropylidenebiphenol (BPA), respectively. These copolymers exhibited molecular weights of up to 36 kDa (as polystyrene equivalents), and were found to be thermally stable with decomposition temperatures in excess of 542℃and relatively high glass transition temperatures (Tg) (152-265℃). UV-vis absorption and fluorescence spectra revealed highly efficient (Φf=0.41-0.66) yellow-green emission (λem=500-514nm) from these materials.