A kinetic study of butyl acrylate free radical polymerization in benzene solution

The free radical polymerization of butyl acrylate has been studied in benzene solutions ranging from 1 to 5 mol·L^–1 at 50°C using 2,2′‐azobisisobutyronitrile as initiator. Under the conditions of our experiments, both the effective rate coefficient for initiation, 2 f k_d , and the coupled parameter, k_p/k_t^1/2, (where k_p and k_t are the constants for propagation and termination reactions, respectively) are dependent on the monomer concentration. The 2 f k_d value shows little increase with monomer concentration. The variation of the k_p/k_t^1/2 parameter has been correlated with the chain length dependence of the termination rate coefficient. This effect is also responsible for the high dependence of the overall polymerization rate, R_p, onthe monomer concentration (1.49).