Kinetic Study of the Polymerization of Diallyl Carbonate

The polymerization of diallyl carbonate was carried out at 60°C, benzoyl peroxide being used as the initiator; here it has been discussed kinetically from the point of view of cyclopolymerization. The rate of polymerization, Rp, was not proportional to the square root or the first power of the initiator concentration, (I), but Rp/(I)1⁄2 and (I)1⁄2 bore a linear relationship. The rate of polymerization, the residual unsaturation, and the degree of polymerization decreased with a decrease in the monomer concentration. The relation between the rate of polymerization over the degree of polymerization, Rp/,o and the monomer concentration, (M), was also linear, as in Rp/(I)1⁄2 and (I)1⁄2. The ratio of the rate constant of the unimolecular cyclization reaction to that of the bimolecular propagation reaction of the uncyclized radical, Kc, was estimated to be 4.0 mol/l from the dependence of the residual unsaturation on the monomer concentration.