γ-radiation-initiated post-polymerization of methacrylic acid in solid state

Abstract The solid‐state postpolymerization of slowly crystallized methacrylic acid was studied at 0°C with 60 Co γ‐radiation as the initiator. The yield, molecular weight, molecular weight distribution, and stereosequencing of the polymer product were determined as a function of polymerization time. The narrow molecular weight distribution and the linear dependence of molecular weight on polymer yield were attributed to a polymerization mechanism characterized by both independent chain propagation and essentially no termination step. The overall polymerization rate was substantially faster than that reported previously for shock‐crystallized monomer, a result which was attributed to termination by the occlusion of propagating radicals at defects in the shock‐crystallized monomer. Although largely atactic, the polymer synthesized in the solid state contained a secondary kind of stereosequencing; the meso triad probability was highest at the end of the chain, where propagation had initiated and decreased continuously with chain growth. The gradient in stereosequencing along the chains was attributed to defects that were introduced into the monomer crystals by the growing polymer chains.