A theoretical description of a method for model-independent determination of bimolecular chain-length-dependent free-radical-termination rate coefficients

J.B.L. Kock, de, B. Klumperman, A.M. Herk, van, A.L. German

Research output: Contribution to journalArticleAcademicpeer-review

47 Citations (Scopus)
120 Downloads (Pure)

Abstract

A theoretical description is given of a method for model-independent determination of bimolecular chain-length-dependent free-radical-termination rate coefficients. By on-line determination of the monomer concentration versus time in a time-resolved pulsed laser polymerization, the value of the termination rate coefficient kti,i of the termination reaction between species of identical chain length can be determined in a very simple fashion. The key assumption in this kt determination is that the radical chain-length distribution that is generated with a laser pulse is extremely narrow, such that all chains can be considered as being identical in chain length. With computer simulations the effects of several processes which could undermine this key assumption were investigated. For the monomer methyl methacrylate (MMA) the effects of (i) a Poisson distribution of the polymerization events, (ii) chain transfer to monomer, and (iii) the presence of a background initiation process were investigated. For MMA, none of these processes interfere with the model-independent determination of the termination rate coefficients, as long as suitable experimental conditions are chosen, which follow from the simulations.
Original languageEnglish
Pages (from-to)6743-6753
JournalMacromolecules
Volume30
Issue number22
DOIs
Publication statusPublished - 1997

Fingerprint

Dive into the research topics of 'A theoretical description of a method for model-independent determination of bimolecular chain-length-dependent free-radical-termination rate coefficients'. Together they form a unique fingerprint.

Cite this