Polymerization of acenaphthylene in solution at high pressures

Abstract

The rate of radical polymerization of acenaphthylene in solution at 60° has been measured from 1–3900 atm. The pressure-coefficient of the rate is much smaller than in the polymerization of other olefinic monomers. The values of the exponents of the monomer and initiator concentrations in the rate equation indicate that there is some degradative chain transfer with monomer molecules, and it is shown that if the kinetic equation for polymerization is modified to include the degradative transfer reaction a smaller pressure-coefficient is to be expected. The low observed value is probably due in part to this effect and in part to a real difference between the pressure-coefficients of the chain-growth reactions for acenaphthylene and for other monomers.