Abstract
The diffusion-free radiation graft polymerization of styrene onto polyethylene has been studied. The grafting rate shows a dependence on monomer which is far different than what has been assumed. Further, the dependence on monomer changes with increasing dose rate as does the dependence of grafting rate on radiation dose rate. Three different regions of behavior are defined: 1- a low dose rate region where the grafting rate is 1 2 - order in dose rate and 3 2 - order in monomer, 2- an intermediate dose rate region where the grafting rate is intermediate between 1 2 - and 0-order in dose rate and 5 2 - order in monomer, and 3- a high dose rate region where the grafting rate is independent of dose rate and at least 5 2 - order in monomer. Various possible mechanisms responsible for these effects are discussed, including the effects of viscosity on the initiation and termination reactions and the possibilities of ionic graft polymerization and energy transfer.
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