Methyl Radical Induced Polymerization of Gaseous Butadiene

Free methyl radicals from thermally decomposing di-t-butyl peroxide were used to initiate the polymerization of gaseous butadiene. The rate of polymerization was found to follow the equation —d[M]/dt = kp(ki/kt)½[M][C]½, where kp, ki, and kt refer to the rate constants for propagation, initiation, and termination, respectively; M and C refer to butadiene and peroxide. From the effect of temperature on the over-all rate constant and the known values of Ei and Et, the value of Ep, the activation energy for chain propagation, was found to be 2.6 kcal/mole.