Behavior of 3‐vinylpyridine in nitroxide‐mediated radical polymerization: The influence of nitroxide concentration,solvent, and temperature

The influence of nitroxide concentration, solvent, and temperature on the nitroxide‐mediated radical polymerization of 3‐vinylpyridine (3VP) was examined. Long‐chain poly(3‐vinylpyridine)s with low polydispersities were synthesized. The initial 2,2,6,6‐tetramethylpiperidin‐1‐oxyl concentration had no influence on the kinetics of the polymerization but was responsible for the obtained molar weights. Compared with the polymerization of styrene, the polymerization of 3VP proved quite fast. The influence of temperature on the reaction rate was also demonstrated, and the polymerization could be controlled even at 110 °C. Some polymerizations were also performed in solution to test the influence of a solvent such as ethylene–glycol, whose effect on the polymerization of 3VP was dependent on temperature. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 3067–3073, 2000