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Chain‐length dependent termination in rotating sector polymerization, 1. The evaluation of the rate constant of chain propagation k p
Author(s) -
Olaj Oskar Friedrich,
Kornherr Andreas,
Zifferer Gerhard
Publication year - 1999
Publication title -
macromolecular theory and simulations
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.37
H-Index - 56
eISSN - 1521-3919
pISSN - 1022-1344
DOI - 10.1002/(sici)1521-3919(19991101)8:6<561::aid-mats561>3.0.co;2-8
Subject(s) - inflection point , chain (unit) , constant (computer programming) , polymerization , polymer , chain termination , chemistry , thermodynamics , order (exchange) , reaction rate constant , materials science , polymer chemistry , physics , mathematics , kinetics , radical polymerization , organic chemistry , geometry , classical mechanics , quantum mechanics , computer science , finance , economics , programming language
The chain‐length distributions (CLDs) of polymers prepared by rotating‐sector (RS) techniques under pseudostationary conditions were simulated for the case of chain‐length dependent termination and analysed for their suitability of determining the rate constant of chain propagation k p from the positions of their points of inflection. The tendency to underestimate k p is a little more pronounced than in pulsed‐laser polymerization (PLP) but, interestingly, the situation improves in the presence of chain‐length dependent termination. The estimates also were found to be more precise a) for smaller rates of initiation, b) for higher order points of inflection, c) if termination is by combination, d) if the role played by the shorter one of the two chains becomes less dominant. Taken in all, the determination of k p from the points of inflection in the CLD of RS‐prepared polymers may well compete with the more famous PLP method, especially if some care is taken with respect to the choice of experimental conditions.