Novel photoconductive and electroactive polymers by metathesis polymerization = 메타세시스 중합에의한 광전도성과 전기활성을 가지는 새로운 고분자의 합성과 그의 응용

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A new photoconductive polymer, poly[Bis(N-carbazolyl)-n-hexyl dipropargyl malonate], poly(BCHDPM), and poly[Bis(N-carbazolyl)-n-hexyl dipropargyl malonate-co-diethyl dipropargyl malonate], poly(BCHDPM-co-DEDPM), were synthesized by metathesis polymerization with various transition metal catalyst systems. The resulting polymers have relatively high molecular weights and exhibited good solubility in common organic solvents such as chloroform, tetrahydrofuran(THF), dimethylformamide (DMF), etc and had surprisingly good stability in air. These conjugated polymers also easily cast on glass plates to give violet-shiny thin films. The structure and properties of the polymer obtained were analyzed by IR, NMR, and UV-Vis spectroscopy. The photo- to dark-conductivity ratio without doping agent was found to be in the range of 30-50 at the $10^3-10^5$(V/cm) and photovoltaic response was also observed. The resulting polymer has a long tail band at above 700nm, suggesting the intramolecular charge transfer complexes between the carbazole groups and the conjugated double bonds in the main chain. The dependences of photocurrent density($\mbox{J_{ph}}$) on the electric field(E), the light intensity(I), and exciting wavelength(I) were also examined. Voltametric measurements showed that solution-cast films of these polymers had two oxidation peaks at 0.98V and 1.32V due to the dicarbazyls from the carbazole units in side chain of the polymers, and also well defined and stable electrochemical activity. The redox kinetics was mainly controlled by ClO$_4$ diffusion processes preserving the electro-neutrality of the polymer. It was found that the redox reactivity of poly(BCHDPM-co-DEDPM) is better than poly(BCHDPM). The color of the poly(BCHDPM-co-DEDPM) changed from transparent light-yellow in reduction state to dark-green in oxidation state, respectively.
Park, Joon-TaikresearcherChoi, Sam-Kwonresearcher박준택researcher최삼권researcher
한국과학기술원 : 화학과,
Issue Date
68938/325007 / 000915813

학위논문(박사) - 한국과학기술원 : 화학과, 1994.2, [ 122 p. ]

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