Fast controlled radical polymerization of styrene mediated by oligomeric nitroxides formed in situ

In the presence of an oligomeric hindered secondary amine added with peracetic acid as the oxidant, radical polymerization of styrene is fast and controlled at 110 degrees C. Under these experimental conditions, an oligomeric nitroxide is formed in situ. This polymerization is 2.5 faster than polymerization mediated by the alkoxyamine derivated from TIPNO (2,2,5-trimethyl-4- phenyl-3-azahexane-3-nitroxide), which generates a low molar mass nitroxide. Similarly, substitution of a low molar mass secondary amine, 2,2,6, 6-tetramethylpiperidone (4-oxo-TMP), for the oligomeric secondary amine maintains the control on the polymerization, which is however 4.6 times slower, all the other conditions being the same. The in situ formation of the oligomeric nitroxide has been confirmed by electron spin resonance (ESR).