No abstract

The degradation rates of free radical polymerized and syn‐diotactic poly(methyl methacrylate) (PMMA) under electron radiation were explored at temperatures ranging from 225 to 325°C and at electron dose rates from 10,000 rads/min to 100,000 rads/min. Scission of bonds between main‐chain atoms resulted in pairs of radical chain ends, of which some disportionated, thereby reducing polymer molecular weight without loss of volatile, while others proceeded to depropagate via the usual radical transfer, causing complete volatilization of the chain without significant change of molecular weight of the residual polymer. Electron irradiation at a dose rate of 100,000 rads/min produced a significant enhancement in the reaction, rate, and reduced the overall activation energy from 140 KJ/g‐mole observed for thermally induced depropagation to a value of 75 KJ/g‐mole observed during simultaneous irradiation and/thermal depropagation.