| Abstract: | Autopolymerization of styrene‐N‐butylmaleimide mixtures at 125 or 140°C in the presence of a stable nitroxyl radical 2,2,6,6‐tetramethylpiperidin‐1‐yloxyl (TEMPO)] was found to proceed in a pseudoliving manner. Unimolecular initiators, which were originated by trapping self‐generated radical species with TEMPO, took part in the process. Under the studied experimental conditions, the TEMPO‐controlled autopolymerization with a varying comonomer ratio provided virtually alternating copolymers of narrow molecular weight distributions. The molecular weights of the copolymers increased with conversions. The obtained styrene‐N‐butylmaleimide copolymers containing TEMPO end groups were used to initiate the polymerization of styrene. The polymerization yielded poly(styrene‐co‐N‐butylmaleimide)‐polystyrene block copolymers with various polystyrene chain lengths and narrow molecular weight distributions. The compositions, molecular weights, and molecular weight distributions of the synthesized block copolymers and the initial poly(styrene‐co‐N‐butylmaleimide) precursors were evaluated using nitrogen analysis, gel permeation chromatography, and 1H‐ and 13C‐NMR spectroscopy. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2378–2385, 1999 |
