Propagation and Termination Rate Constants of N-tert-Alkyl- and N-Trialkylsilylmaleimides in Radical Polymerization Initiated with 2,2′-Azobisisobutyronitrile

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Radical polymerizations of N-tert-alkylmaleimide (tRMI) and N-trialkylsilyl-maleimide (RSiMI) were investigated kinetically by means of electron spin resonance (ESR) spectroscopy. By the use of the steady-state concentrations of the polymer radicals determined by ESR, the propagation and termination rate constants (kp and kt) were evaluated. kt was also determined by analysis of the non-steady state. tRMI and RSiMI were revealed to have similar kp depending on the bulkiness of the N-substituents, while kt for RSiMI were about ten times larger than those for tRMI. The relationships between kp and kt values and the structure of the N-substituents were discussed.