The Cyclopolymerization of Triallyl Citrate

The radical polymerization of triallyl citrate was carried out at 60 °C, benzoyl peroxide being used as the initiator and benzene as the solvent; here it has been considered kinetically in terms of cyclopolymerization. Thus, the kinetic equations for the polymerization of the triallyl ester were first derived by an extension of the kinetic treatment for the cyclopolymerization of the diallyl ester. Next, they were applied to the polymerization of triallyl citrate. In consequence, the following results were obtained: (i) the rate of polymerization, Rp, was not proportional to either the square root or first power of the initiator concentration, [I]; rather, Rp/[I]1⁄2 and [I]1⁄2had a linear relationship, (ii) the relation between the rate of polymerization over the degree of polymerization, Rp/,o, and the monomer concentration, [M], was also linear, and (iii) the ratio of the unimolecular cyclization reaction to the bimolecular propagation reaction of the uncyclized radical, Kc, was estimated to be 4.5 mol/1 from the dependence of the residual unsaturation on the monomer concentration.