1415217-68-3Relevant academic research and scientific papers
Synthesis and postfunctionalization of rod-coil diblock and coil-rod-coil triblock copolymers composed of poly(3-hexylthiophene) and poly(4-(4′-N, N -dihexylaminophenylethynyl)styrene) segments
Fujita, Hiroyuki,Michinobu, Tsuyoshi,Tokita, Masatoshi,Ueda, Mitsuru,Higashihara, Tomoya
, p. 9643 - 9656 (2012)
Poly(3-hexylthiophene) (P3HT) with a bromobutyl functional group at the ω-chain-end (P3HT-C4Br) and P3HT with bromobutyl functional groups at the α,ω-chain-ends (BrC4-P3HT-C4Br) were synthesized by selecting the appropriate initiators for the Grignard metathesis (GRIM) polymerization. The high end-functionality was confirmed by matrix assisted laser desorption-ionization time-of-flight (MALDI-TOF) mass spectrometry. These polymers were efficiently reacted with the living anionic polymers of 4-(4′-N,N-dihexylaminophenylethynyl)styrene (DHPS) to yield novel rod-coil diblock and coil-rod-coil triblock copolymers composed of rigid P3HT and flexible poly(4-(4′-N,N-dihexylaminophenylethynyl)styrene) (PDHPS) segments. The expected structures of the block copolymers were confirmed by size exclusion chromatography (SEC), proton nuclear magnetic resonance (1H NMR), and Fourier transform infrared (FT-IR) spectroscopies. Furthermore, the side chain alkynes of the PDHPS segments of both P3HT-b-PDHPS and PDHPS-b-P3HT-b-PDHPS were quantitatively functionalized by a [2 + 2] cycloaddition followed by a cycloreversion with tetracyanoethylene (TCNE), producing the corresponding block copolymers with donor-acceptor moieties in the flexible polystyrene segments. The formation of the new chromophores was confirmed by UV-vis spectroscopy and cyclic voltammetry (CV), which revealed strong intramolecular charge-transfer bands and redox activities ascribed to the formed donor-acceptor moieties. The thermal properties and surface morphology of the block copolymers were also evaluated by differential scanning calorimetry (DSC), atomic force microscopy (AFM) observations, and small-angle and wide-angle X-ray scattering (SAXS and WAXS). This is the first report about the development of P3HT-based block copolymers with tunable optoelectronic properties, which was achieved by the combined synthetic techniques of the GRIM polymerization, living anionic polymerization, and click postfunctionalization.
