Pyrolysis mass spectrometric analysis of copolymer of polyacrylonitrile and polythiophene


Tezin Türü: Yüksek Lisans

Tezin Yürütüldüğü Kurum: Orta Doğu Teknik Üniversitesi, Fen Edebiyat Fakültesi, Kimya Bölümü, Türkiye

Tezin Onay Tarihi: 2004

Öğrenci: GÜLCAN OĞUZ

Danışman: JALE HACALOĞLU

Özet:

In the first part of this work, the structural and thermal characteristics of polyacrylonitrile, polyacrylonitrile films treated under the electrolysis conditions in the absence of thiophene, polythiophene and the mechanical mixture and a conducting copolymer of polyacrylonitrile/polythiophene have been studied by pyrolysis mass spectrometry technique. The thermal degradation of polyacrylonitrile occurs in three steps; evolution of HCN, monomer, low molecular weight oligomers due to random chain cleavages are followed by cyclization and dehydrogenation reactions yielding crosslinked and unsaturated segments. Pyrolysis of the treated polyacrylonitrile films indicated decrease in the yields of monomer and oligomers, and increase in the amount of products stabilized by cyclization reactions were detected. Polythiophene degrades in two steps; the loss of the dopant and degradation of polymer backbone. The evolution profiles of polythiophene based products from polythiophene/polyacrylonitrile showed nearly identical trends with those recorded during the pyrolysis of pure polythiophene. However, evolution of HCN and the degradation products due to the homolytic cleavages of the polymer backbone continued through out the pyrolysis indicating a significant increase in their production. Furthermore, the yield of thermal degradation products associated with decomposition of the unsaturated cyclic imine segments decreased. A careful analysis of the data pointed out presence of mixed dimers confirming copolymer formation. In the second part of this work, a poly(acrylonitrile-co-butadiene) sample involving monomer units having quite similar molecular weights have been analyzed to investigate the limits of the pyrolysis mass spectrometry technique. Pyrolysis of aged poly(acrylonitrile-co-butadiene) indicated oxidative degradation of the sample. Keywords: conducting copolymer,