Synthesis And Characterization Of Conducting Polymers Functionalized With Acrylic Monomer

Electrochemical polymerization has been tested as one of the most effective way for the prepration of high-quanlity conducting polymers. It is very difficult to prepare freestanding and conducting polymer films by direct anodic oxidation of aromatic monomers. Therefore, the preparation of freestanding and conducting polymer films became a great challenge. Previous studies have indicated that the incorporation of traditional polymer backbone, such as polyethylene chain into the extented conjugated chain can be helpful for high quality film formation. As a consequence, various aromatic functionalized with acrylate units have been synthesized. In this dissertation, novel acrylate functionalized monmers with pendant carbazole and fluorene units were synthesized, respectively. The radical polymerizations of synthesized acrylate monomers functionalized with pendant electroactive units led to the formations of precursor polymers. Then free-standing and conducting conjugated polymer network films were synthesized electrochemically by direct anodic oxidation of precursor polymers. The as-formed conjugated polymer network films showed good electrochemical behavior and high thermal stability, and were characterized by UV-Vis, FT-IR and fluorescence spectral analyses. At the same time, the influene of different alkyl chain length on the electrochemical polymerization of carbazole which acrylic functionalized and polymer properties were studied.1. A novel acrylate functionalized with pendant fluorene monomer, 9H-fluoren-9-acrylate(FA) was designed and successfully synthesized. Precursor polymers were prepared by the radical polymerization of the monomer. High quality freestanding polyfluorene network films were synthesized successfully in CH2Cl2 containing additional 40% (by volume) BFEE by direct anodic oxidation of its precursor polymer. The possibility of inter- and intra-molecular polymerization resulted in a crosslinked conjugated network microstructure. UV-visible and FT-IR spectra were used to study the structures of the polymers, respectively. The maximum emission peak of PFA appeared at 346 nm while that of PPFA in solid state appeared at 415 nm, implying the blue-light emitting property of PPFA. Polyfluorene network films obtained from this medium showed thermal stability significantly improved. 2. A novel acrylate functionalized with pendant fluorene monomer, N-9H-fluoren-9-acrylamide (FAM) was designed and successfully synthesized. High quality freestanding polyfluorene network films were synthesized successfully in BFEE by direct anodic oxidation of its precursor polymer, a polyacrylate functionalized with fluorene, which was firstly obtained through radical polymerization of fluorene acrylate. Polyfluorene network films obtained from this medium showed good electrochemical behavior and high thermal stability. The possibility of inter- and intra-molecular polymerization resulted in a crosslinked conjugated network microstructure. UV-visible and FT-IR spectra were used to study the structures of the polymers, respectively. The maximum emission peak of PFAM appeared at 346 nm while that of PPFAM in solid state appeared at 415 nm, implying the blue-light emitting property of PPFAM.3. A novel acrylate functionalized with pendant carbazole monomer, N-[6-(acryloxy)hexyl]carbazole (MACZ6), was synthesized. The radical polymerization of MACZ6 led to the formation of a precursor polymer, poly(N-[6-(acryloxy)hexyl]carbazole) (PMACZ6). Free-standing and conducting conjugated polycarbazole network poly-{poly(N-[6-(acryloxy)hexyl]carbazole)} (PPMACZ6) films were synthesized electrochemically by direct anodic oxidation of PMACZ6, showing good electrochemical behavior and high thermal stability with conductivity of 1.34×10-5 S cm-1. The obtained network polymer films were characterized by UV-vis, FT-IR and fluorescence spectral analyses and the fluorescence spectral studies revealed that the PPMACZ films were good blue light emitters.4. Two novel acrylate functionalized monomers N-[10-(Acryloxy)decyl]carbazole (MACZ10),N-[12-(Acryloxy)dodecyl]carbazole (MACZ12), which incorporate a carbazole moiety at the terminal of the hydrocarbon chain, were designed and synthesized. Through radical polymerization of MACZ led to the formation of two precursor polymers, poly(N-[10-(Acryloxy)decyl]carbazole) (PMACZ10) and poly(N-[12-(Acryloxy)dodecyl]carbazole) (PMACZ12) were prepared. The results of GPC indicated that the molecular weights of the two precusor polymers decreased with the increase the alkyl chain length. Fluorescence spectral showed that the esmission intensity of peak at 353 nm of the precusor polymers decreased with the increase the alkyl chain length. Free-standing and conducting conjugated polycarbazole network poly-{poly(N-[10-(Acryloxy)decyl]carbazole)} (PPMACZ10) and poly-{poly(N-[12-(Acryloxy)dodecyl]carbazole)} (PPMACZ12) films were synthesized electrochemically by direct anodic oxidation of PMACZ10 and PMACZ12 in THF containing additional 10% (by volume) BFEE. PPMACZ films obtained from this medium showed good electrochemical behavior and good thermal stability. As-formed PPMACZ films were characterized by UV-Vis, FT-IR, and fluorescence spectral analyses. Fluorescence spectral studies revealed that PPMACZ films were good blue light emitters. And with the increase of alkyl chain length, the reversible redox polymer increased and emission peak became broadens.