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Kinetic Features of Three-Dimensional Free-Radical Polymerization

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Three-Dimensional Free-Radical Polymerization

Abstract

Key results of systematic exploration into three-dimensional free-radical polymerization (TFRP) in blocks, solutions, and films carried out by the authors are described in Chap. 2. An interpretation of TFRP kinetic features takes the microheterogeneous mechanics of polymerization into account. The factors determining the effective reactivity of unsaturated oligomers (allyl and vinyl types) under different conditions and at various TFRP stages were identified. All this enabled the authors to create a scientific basis of control over TFRP needed to produce different-purpose polymeric materials.

The main kinetic features of TFRP were determined in a series of systematic studies conducted by the authors with the use of oligo(acrylates) starting in 1960 [1–5]. Oligo(acrylates) were found to be very convenient oligomers for such experiments because their synthesis method enables us to vary, as targets, chemical composition and oligomer block size in a wide range, with the end methacrylate or acrylate groups able to polymerize being invariable [1,3].

Processes of TFRP for polyunsaturated oligomers (monomers) of various structures have a similar development pattern. At the initial stage (in nonstructured reaction medium), the polymerization rate W0 remains constant in a rather narrow range of conversions, 0 < C < 3–4%; then, in the period of polymerization auto-acceleration, it increases with growing C, and then with conversion Cmax, it becomes maximal Wmax. Subsequently, polymerization auto-deceleration takes place with complete TFRP process termination when limit conversion Clim < 100%. During periods of auto-acceleration and auto-deceleration, polymerization proceeds in a structured reaction medium. The analysis of main kinetic TFRP features requires identifying factors determining the effective reactivity of oligomers (monomers) at each consecutive stage of the process as well as in different TFRP conditions (in the presence of inhibitors, in solutions, and in films).

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Authors and Affiliations

  1. Russian Academy of Sciences, Russia

    Gennady V. Korolev (Prof.Dr)

  2. Kaznacheyskaya ulitca, Dom 13, flat 1, 198031, St. Petersburg, Russia

    Michael M. Mogilevich (Prof.Dr)

Authors
  1. Gennady V. Korolev
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  2. Michael M. Mogilevich
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Korolev, G.V., Mogilevich, M.M. (2009). Kinetic Features of Three-Dimensional Free-Radical Polymerization. In: Three-Dimensional Free-Radical Polymerization. Springer, Berlin, Heidelberg. https://doi.org/10.1007/978-3-540-87567-3_2

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