Synthesis of Poly(N‐vinylamide)s and Poly(vinylamine)s and Their Block Copolymers by Organotellurium‐Mediated Radical Polymerization

Abstract Controlled polymerization of acyclic N ‐vinylamides, that is, N ‐methyl‐ N ‐vinylacetamide (NMVA), N ‐vinylacetamide (NVA), and N ‐vinylformamide (NVF), by organotellurium‐mediated radical polymerization (TERP) is reported. The corresponding poly( N ‐vinylamide)s with controlled molecular weight and low dispersity ( Ð <1.25) were obtained with high monomer conversion in all cases. This is the first report on the controlled polymerization of NVF. Hydrolysis of the polymers, in particular PNVF, occurred quantitatively under mild reaction conditions, giving structurally controlled poly(vinylamine)s. Block copolymers containing poly( N ‐vinylamide) and poly(vinylamine) segments were also synthesized in a controlled manner.