Non-ideal polymerization. Treatment of non-ideality due to primary radical termination and degradative chain transfer

Abstract

A method is proposed for analysing the problems associated with non-ideal polymerizations reflected mainly in the variability of R p /[I] 0·5[M] where R p is the rate of polymerization and [I] and [M] are the initiator and monomer concentrations, respectively. Primary radical termination and degradative chain transfer are treated jointly and the entirely different mathematical natures of the two processes are described. The method could dispense with the need to use the uninhibited rate of polymerization which does not lend itself to reliable measurements for many systems. It is found to be efficient in detecting the active species in a polymerization system that leads to non-ideality due to degradative chain transfer. This method is applied to vinyl chloride polymerization data from the literature, the values of constants obtained therefrom are found to agree well with the existing values.