Abstract
The mechanism of chain propagation and termination in post-polymerization of N-phenylmaleimide in poly-crystalline samples and in single crystals, has been studied by the EPR method and by diathermic calorimetry. It is shown from the anisotropy of the EPR spectra of growing macroradicals R p that oriented growth of the polymer chains occurs at low degrees of conversion ( θ⪅3%) and subsequently the matrix becomes amorphous. It is shown that migration of the radical group R p occurs as a result of growth of the polymer chain. By means of the method based on the kinetics of recombination, a method is proposed for determining the reaction volume V R ∗ , i.e. the volume within which the reactants must meet for reaction to occur between them. For recombination of radicals R p it was found that V R ∗≌6×10 −21 cm 3, i.e. the radius of the “reaction” sphere r ∗ R = 3 4π V ∗ R 1 3 ⋍11 A ̊ ⋍1·5 γ .
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