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Kinetics of formation of the topological structure during radical polymerization accompanied by the reaction of chain transfer to the polymer

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Abstract

The structural-kinetic features of radical polymerization accompanied by chain transfer to the polymer are considered in this study. The kinetic equations are solved in a general form without any assumptions. The expression for the critical conversion of gel formation (the gel point), αc, is obtained:

$\alpha _c^{ - 1} = 1 + (1 - \delta )[M]_0 (k_{trp} - (k_{trp} )_c )/k_t [R]$

. The resulting αc values are compared with the data calculated through the monoradical approach, when it was assumed that the steady-state approximation not only for total radical concentration [R] but also for macroradical concentration [R i ] can be used. A close agreement between the results is demonstrated. This fact means that the latter approach can be used to analyze the kinetics of the process. The main topological characteristics of the polymer are obtained: the molecular-mass distribution and the distribution of macro-molecules over the degrees of branching.

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Authors and Affiliations

  1. Institute of Problems of Chemical Physics, Russian Academy of Sciences, pr. Akademika Semenova 1, Chernogolovka, Moscow oblast, 142432, Russia

    T. F. Irzhak & V. I. Irzhak

Authors
  1. T. F. Irzhak
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  2. V. I. Irzhak
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Correspondence to V. I. Irzhak.

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Original Russian Text © T.F. Irzhak, V.I. Irzhak, 2013, published in Russian in Vysokomolekulyarnye Soedineniya, Ser. B, 2013, Vol. 55, No. 6, pp. 755–763.

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Irzhak, T.F., Irzhak, V.I. Kinetics of formation of the topological structure during radical polymerization accompanied by the reaction of chain transfer to the polymer. Polym. Sci. Ser. B 55, 391–399 (2013). https://doi.org/10.1134/S1560090413060043

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