Design of well-defined monofunctionalized poly(3-hexylthiophene)s: toward the synthesis of semiconducting graft copolymers.

The post-functionalization of poly(3-hexylthiophene) (P3HT) via various synthetic routes is reported. Well-defined and monofunctionalized ω-thiol-terminated P3HT, ω-carboxylic acid-terminated P3HT, ω-acrylate-terminated P3HT, and ω-methacrylate-terminated P3HT are obtained in high yields through a straightforward procedure. From those, different novel P3HT-based graft copolymers are synthesized following two routes: "grafting onto" and "grafting through" (macromonomer polymerization) methods. The synthesis of three types of graft copolymers is described. Each one has "rod" P3HT-grafted side chains on a "coil" main chain, which can be polyisoprene, poly(vinyl alcohol), or poly(butyl acrylate). Each copolymer is characterized by size-exclusion chromatography and NMR.