Abstract
The kinetic laws governing the radiation polymerization of vinyl monomers in previously formed three-dimensional networks are studied by a calorimetric method. It is shown that the polymerization of styrene and methyl methacrylate starts immediately after the gel-effect stage. With both monomers a bimolecular mechanism applies to the detachment of microradicals. Non-steady-state kinetic measurements are made over a wide range of degrees of conversion, and the rate constants for chain propagation and termination are calculated. The chain propagation rate constant for the polymerization of styrene and methyl methacrylate in networks is identical with the corresponding rate constant for the bulk polymerization of these monomers, and the chain termination rate constant is three orders less than that for block polymerization, which results in earlier appearance of the gel-effect.
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