Decomposition of peroxycarbamates and their initiation of vinyl polymerization

A review is given of the synthesis, physical properties, and decomposition kinetics of organic peroxycarbamates. The activity of these compounds in initiating free-radical vinyl polymerization is discussed. The decomposition of hexamethylene N,N′-bis-(α-cumyl peroxycarbamate) has been measured in different solvents between 65 and 95°C and found to be a first-order reaction governed by the specific rate constant k_d = 2.21 × 10¹⁶ exp {?34 100/RT}. The initiator exhibits normal free-radical polymerization kinetics and in polymerization of styrene at 80°C shows an initiating efficiency of 0.53. Cobalt naphthenate can act as both accelerator and retarder of styrene polymerization, depending upon its concentration and the temperature of the polymerization.