NMR and ESR studies of the solid-state polymerization of vinyl monomers. I. Acrylamide

Abstract The kinetics of the solid‐state polymerization of acrylamide, γ‐irradiated at 77°K, has been studied by wide line NMR and by ESR at temperatures above 300°K. This reaction may be followed by the growth of a narrow line superimposed on the NMR spectrum of the monomer. The amplitude of this narrow line has been found to be proportional to the polymer yield. By long continued annealing, the conversion yield approaches a limiting value, generally lower than 50% under most of our experimental conditions. The activation energy of post‐polymerization is 19 ± 1 kcal/mole. The radiochemical yield of radicals, determined by ESR, is 0.27 ± 0.03 at 77°K before warming. In the course of annealing above 300°K, the overall concentration of radicals is reduced to about one tenth of its initial value at 77°K. However, the local concentration of the remaining radicals is constant and equal to 1.2 × 10 19 spins/g, i.e., more than 100 times their overall concentration. The recombination of radicals does not seem to intervene in the kinetics of post‐polymerization, so that it may be assumed that only the radicals remaining after annealing, have actually contributed to the reaction.