Abstract
AbstractA model is proposed for the interpretation of molecular weight changes occurring in the pregel region of irradiated dilute aqueous polymeric systems. The model is, in principle, related to and gives results compatible with the molecular weight changes occurring during condensation polymerisation. On the basis of the above model and the ZIMM‐KILB theory of branching effects on intrinsic viscosity, calculated intrinsic viscosities agree satisfactorily with results for low molecular weight material only when allowance is made for intramolecular crosslinking and a drastic reduction in the rate of intermolecular crosslinking with dose for doses close to the gel dose. A similar quantitative approach is not possible for higher molecular weight material because of the high branching densities involved. A qualitative approach shows that many features of the radiation induced behaviour of intrinsic viscosities can be explained by the proposed model. For concentrations below the critical concentration, a treatment based on diffusion control of intermolecular crosslinking was found to be satisfactory.
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