THE REACTIVITY OF THE CYCLIC POLYENES TOWARDS FREE RADICALS: I. COPOLYMERIZATION WITH ACRYLONITRILE

Abstract

Cyclohexadiene-1,3 and bicyclo[2.2.1]heptadiene-2,5 each (B) copolymerize with acrylonitrile (A) in bulk at 60 °C in the presence of 0.01 M benzoyl peroxide. The copolymerization parameters for cyclohexadiene-1,3 are rA = 0.026 ± 0.014,rB = 0.20 ± 0.01, QB = 1.76, eB = −1.18; for bicycloheptadiene the parameters are rA = 0.65 ± 0.02, rB = 0.47 ± 0.08, QB = 0.27, eB = 0.03; limits of error are given at the 10% probability level. Cycloheptatriene and cyclooctatetraene inhibit the polymerization of acrylonitrile under similar conditions over a wide range of concentration. These results are discussed in terms of the general reactivity of the cyclic polyenes and of the behavior of structurally related monomers in polymerization, and a consistent pattern of reactivity emerges.