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The nature of the chain-length dependence of the propagation rate coefficient and its effect on the kinetics of free-radical polymerization. 1. Small-molecule studies by Johan P.A. Heuts; Gregory T. Russell is a Materials Science article available to read on EtoBox.
What is The nature of the chain-length dependence of the propagation rate coefficient and its effect on the kinetics of free-radical polymerization. 1. Small-molecule studies about?
In this paper we summarize and analyze the currently available small-molecule data, both experimental and theoretical, that is relevant to chain-length-dependent propagation in free-radical polymerization (FRP). We do this in order to appreciate the nature of chain-length-dependent propagation, because workers are becoming increasingly cognizant of its necessity in reaching a complete understanding of FRP kinetics. We show that studies of addition in small-molecule (model) systems support a chain-length dependence (at short chain lengths i) which is described by the following functional form, which therefore can be said to be physically realistic: , where the values of C 1 and i 1/2 are of the order of 10 and 1, respectively. These results are supported by transition state theory, which predicts a very similar behavior for the Arrhenius frequency factor. We illustrate that in systems with low number-average degree of polymerization (DP n ), this chain-length dependence can dramatically affect the observed (chain-length-averaged) propagation rate coefficient hk p i, which can be significantly higher than the long chain value, k p . However, this effect is only observed if the activa
Who reads The nature of the chain-length dependence of the propagation rate coefficient and its effect on the kinetics of free-radical polymerization. 1. Small-molecule studies?
It is typically read by researchers, students, and practitioners in Materials Science.
- Author
- Johan P.A. Heuts; Gregory T. Russell
- Publisher
- Elsevier Science; Elsevier ; Elsevier Ltd.; Elsevier BV (ISSN 0014-3057)
- Published
- 2006
- Language
- EN
- Field
- Materials Science (Physical Sciences)