Time-dependent reaction rates in the thermolysis of a poly(vinylnaphthalene endoperoxide)

Abstract

Classical reaction kinetics with time-independent rate constants have failed to provide a satisfactory explanation of the rate of thermolysis leading to the release of excited ( 1 Δ g ) molecular oxygen from polymer solutions and thin solid films of 1,4-dimethyl-2-poly(vinylnaphthalene 1,4-endoperoxide). First-order kinetics with time-dependent rates are shown to produce better agreement with the experimental data. The thermolysis rate constant is observed to have the time dependent k∼t α-1 , where α=0.66 for polymer solutions and α=0.38 for polymer thin films. The value of α indicates the di of lifetimes for excited oxygen