Alkyne–azide coupling of tailored poly(vinylidene fluoride) and polystyrene for the synthesis of block copolymers

The synthesis of block copolymers consisting of poly(vinylidene fluoride) (PVDF) and polystyrene (PS) is reported. Firstly, a propargyl-functionalized alkoxyamine initiator (PgOTIPNO) was prepared and subsequently used for the preparation of a propargyl-terminated PS homopolymer of different chain lengths with low dispersities via nitroxide-mediated radical polymerization. A tailored PVDF homopolymer with iodine end groups originating from iodine transfer polymerization was transformed to PVDF with azide end group. Then, alkyne-terminated PS with different molecular weights and azide-terminated PVDF were joined together via copper-catalyzed alkyne–azide coupling. The block copolymers were characterized using 1H-NMR, 19F-NMR, IR, SEC, and DSC.