Gel permeation chromatographic determination of activation rate constants in nitroxide‐controlled free radical polymerization, 1. Direct analysis by peak resolution

Abstract

Abstract The dissociation rate constant k d related to the homolytic cleavage of the CON bond formed between a polystyrene (PS) and 2,2,6,6‐tetramethylpiperidin‐1‐oxyl (TEMPO) is determined by adopting the gel permeation chromatography peak‐resolution method to the styrene polymerization with a PS‐TEMPO adduct as a probe and the radical initiator tert ‐butyl hydroperoxide. The result was given by the Arrhenius equation, k d = A exp(− E /( RT )) with A = 3.0 × 10 13 s −1 and E = 124 kJ · mol −1 .