Preparation and characterization of semiconducting polymeric blends. Photochemical synthesis of poly(3-alkylthiophenes) using host microporous matrices of poly(vinylidene fluoride)

Abstract

Chemical and electrochemical synthesis techniques have been the principal methods of obtaining polymers in industry and scientific research laboratories. However, during the last two decades, photochemical synthesis, although poorly studied, has been reported to present several advantages, in that it is a fast and cheap technique, and it is not aggressive to the environment. The technique has been applied to the production of some conducting polymers. In this study, semiconducting polymeric blends composed of PT3AA-K–PVDF and PT3MA–PVDF were respectively obtained by photochemical polymerization in aqueous solutions of 3-thiophene acetic acid and 3-thiophene methyl acetate monomers using PVDF microporous matrices and potassium dichromate as catalyst. The percentage of products and by-products incorporated in the host matrix was obtained by gravimetric analysis. The chemical structures of the polymers synthesized were analyzed by FTIR, UV-vis and ¹H NMR. GPC analysis indicated the formation of oligomers composed of 5–6 mers. The morphology of the matrices and polymeric blends was observed by SEM-EDS and their electric behavior evaluated by measures of electric conductivity. The SEM images show the presence of polythiophene in the pores of the PVDF microporous membrane. The thermal properties of the polymers and their blends were evaluated by DSC and TGA. Thermal analysis by DSC demonstrated an increase in melting temperature of the blends, attributed to the confinement of PVDF crystalline phases for the polymer photosynthesized. The results of volumetric conductivity measurements of polymeric blends show an increase in conductivity in the matrices from 10⁻¹⁵ to 10⁻¹¹ S cm⁻¹.