Abstract
AbstractThe chain‐length distribution and its moments were calculated for a periodically interrupted photopolymerization with termination by disproportionation and negligible chain transfer. For a wide range of experimental conditions, which are readily accessible in the overwhelming majority of cases, the position of the first point of inflection in the chain‐length distribution corresponds exactly to the quantity kp [M]t0, kp representing propagation rate constant, M monomer and t0 the period length. Thus kp can be directly evaluated from the chain‐length distribution of the polymer. Together with the ratio k/kt, kt being the termination rate constant, calculated from the rate and weight‐average degree of polymerization according to a universal relationship—the validity of which is also verified — resolution into the individual rate constants is easily accomplished. The dependence on experimental conditions of the ratio weight‐ to number‐average degrees of polymerization Pw/Pn, which is a measure of the width of the molecular weight distribution of the polymer formed, is discussed.
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