Abstract

AbstractRegioregular poly(3‐hexyl thiophene) (rr‐P3HT)‐based star polymers were synthesized by a crosslinking reaction of the linear rr‐P3HT macroinitiator and ethylene glycol dimethacrylate (EGDMA) crosslinker through Ru‐based atom transfer radical polymerization (ATRP), where the rr‐P3HT macroinitiator was prepared by Grignard metathesis method (GRIM) followed by end functionalization of the ATRP initiator with chlorophenylacetate (CPA) to the rr‐P3HT. Relatively high molecular weight of the star polymers were obtained (Mp = 8,988,000 g/mol), which consisted of large numbers of the rr‐P3HT arm chains radiating from the EGDMA‐based microgel core. The yield of the star polymers were strongly affected by the added amount of the EGDMA crosslinker. The crystalline structure of the rr‐P3HT by intermolecular π‐π stacking interaction gradually decreased as the star polymer formed, which was confirmed by differential scanning calorimeter (DSC), atomic force microscopy (AFM), and electro‐optical analyses. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011

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