Abstract: | N‐Isopropyl‐4‐vinylbenzylamine (PVBA) was synthesized and used as an initiator for the polymerization of methacrylates to synthesize macromonomers with terminal styrenic moieties. LiPVBA initiated a living polymerization and block copolymerization of methyl methacrylate, 2‐(N,N‐dimethylamino)ethyl methacrylate and tert‐butyl methacrylate and produced polymers having well‐controlled molecular weights and very low polydispersities (M̄w/M̄n < 1.1) in quantitative yield. 1H NMR analysis revealed that the polymers contained terminal 4‐vinylbenzyl groups. The macromonomers were reactive in the copolymerization with styrene. |