High conversion study of living radical polymerization of styrene using DSC

The influence of temperature on nitroxide-controlled living radical polymerization of styrene was examined. It has been established that only in a temperature range of 110°C to 150°C nitroxides are able to control radical polymerization. At temperatures above 160°C the reaction was of rather a free radical character. The results were similar for all the various nitroxides used as capping agents: TEMPO (2,2,6,6-tetra-methylpiperidine-N-oxyl), 4-hydroxy-TEMPO, 4-oxo-TEMPO and 4-acetamido-TEMPO. Differences were found only in the induction times of polymerization and were probably due to side reactions with the initiator (benzoyl peroxide). Living radical polymerization can be best controlled with these nitroxides at temperatures between 120°C and 140°C.