Design of Novel Brush-Shaped π-Conjugated Polymers Based on the Controlled Synthesis of Poly(vinyl ether)s with a Terminal Ethynylbenzene Moiety

Various pi-conjugated polymers have been synthesized for advanced materials possessing electrically-conductive and photoluminescence properties. In this study, for the synthesis of novel pi-conjugated polymers grafted with poly(vinyl ether) pendants by the "grafting through" methodology, a poly(vinyl ether)-based macromonomer bearing a diethynylbenzene group at the terminus (DE-PIBVE) was synthesized. First, the macromonomer was synthesized by living cationic polymerization of isobutyl vinyl ether using a diethynylbenzene-appended initiator (TMS-DEVE-TFA) in conjunction with EtAlCl2 and dioxane, followed by deprotection with TBAF. Then, oxidative coupling reaction of the terminal diethynylbenzene group of DE-PIBVE afforded the target brush-shaped polymer having a poly(phenylene butadiynylene) backbone [Poly(DE-PIBVE)].