Facile Preparation of Regioregular Poly(3-hexylthiophene) and Its Block Copolymers with π-Allylnickel Complex as External Initiator

Abstract

Simply prepared π-allylnickel complexes were used as external initiators for promoting the polymerization of 2-bromo-3-hexyl-5-chloromagnesiothiophene in a living/controlled chain growth manner to afford regioregular poly(3-hexylthiophene) with an allyl terminus. The nickel species on the other chain end can initiate the block copolymerization of hexadecyloxylallene and 2-bromo-3-hexyl-5-chloromagnesiothiophene to give a well-defined triblock copolymer containing poly(3-hexylthiophene) and poly(hexadecyloxylallene) segments in one pot via mechanically distinct, sequential living polymerization. Furthermore, such π-allylnickel(II) complexes can also catalyze the polymerization of a range of vinyl monomers, including styrene, 1-methoxy-4-vinylbenzene, and 1-chloro-4-vinylbenzene as well as tert-butyl acrylate, in living/controlled fashion. The active nickel unit at the growing chain end of these vinyl polymers can also initiate the block copolymerization of 2-bromo-3-hexyl-5-chloromagnesiothiophene to give ...