Conjugated block copolymers via functionalized initiators and click chemistry


Smith, K.A.; Pickel, D.L.; Yager, K.G.; Kisslinger, K.; Verduzco, R. "Conjugated block copolymers via functionalized initiators and click chemistry" Journal of Polymer Science Part A: Polymer Chemistry 2014, 52 154–163.
doi: 10.1002/pola.26984


Novel block-copolymers are reported.


Conjugated block copolymers are potentially useful for organic electronic applications and the study of interfacial charge and energy transfer processes; yet few synthetic methods are available to prepare polymers with well-defined conjugated blocks. Here, we report the synthesis and thin film morphology of a series of conjugated poly(3-hexylthiophene)-block-poly(9,9-dioctylfluorene) (P3HT-b-PF) and poly(3-dodecylthiophene)-block-poly(9,9-dioctylfluorene) (P3DDT-b-PF) block copolymers prepared by functional external initiators and click chemistry. Functional group control is quantified by proton nuclear magnetic resonance spectroscopy, size-exclusion chromatography, and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry. The thin film morphology of the resulting all-conjugated block copolymers is analyzed by a combination of grazing-incidence X-ray scattering, atomic force microscopy, and transmission electron microscopy. Crystallization of the P3HT or P3DDT blocks is present in thin films for all materials studied, and P3DDT-b-PF films exhibit significant PF/P3DDT co-crystallization. Processing conditions are found to impact thin film crystallinity and orientation of the ?–? stacking direction of polymer crystallites.