Abstract
1. The influence of pressure upon the rate and average degree of polymerization of styrene was investigated in benzene solution, in butyraldehyde, and in two mixtures of these substances at 50° in the presence of azoisobutyrodinitrile. The rate and average degree of polymerization in benzene solution increase 4.2- and 6.5-fold, respectively, when the pressure is raised from atmospheric to 2000 kg/cm2. The value of the pressure decreases with increasing butyraldehyde content in the mixture. 2. On the basis of data on the influence of pressure upon the rate and average degree of polymerization of styrene in benzene we calculated the value of the volume activation effect in the case of initiation (ΔVin≠) at atmospheric pressure. This value (+ 7.4 cm3/mole) proved close to the value of ΔVin≠ cited in the literature for the decomposition of azoisobutyrodinitrile in toluene solution at 62.5° (+ 9.4 cm3/mole). 3. An investigation of the dependence of the average degree of polymerization on the butyraldehyde: styrene ratio at various pressures led to the conclusion that the rate constant of chain propagation during the polymerization of styrene increases with increasing pressure to a substantially greater degree than the rate constant of chain transfer through butyraldehyde.
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