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Determination of reactivity ratios in copolymerization
Author(s) -
O'Driscoll K. F.,
Reilly P. M.
Publication year - 1987
Publication title -
makromolekulare chemie. macromolecular symposia
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.257
H-Index - 76
eISSN - 1521-3900
pISSN - 0258-0322
DOI - 10.1002/masy.19870100118
Subject(s) - reactivity (psychology) , copolymer , correctness , monomer , computer science , set (abstract data type) , chemistry , mathematics , polymer chemistry , algorithm , organic chemistry , polymer , medicine , alternative medicine , pathology , programming language
Free radical copolymerization of two monomers is usually described in terms of reactivity ratios, only two of which are needed for the simplest (Mayo‐Lewis) model. Other, more complex models (such as penultimate unit effects or complex formation) require more kinetic parameters for a complete description. Published summaries of reactivity ratios list values for about 700 monomers taken from more than 1400 publications. These values represent an enormous amount of descriptive and physico‐chemical information about copolymerization in particular and free radical reactivity in general. It is important that we understand the limits to the numerical correctness of existing data, and that future data gathering be done in a statistically correct manner. In this paper several different linear and non‐linear regression approaches to estimating reactivity ratios are reviewed with emphasis being placed on the Mayo‐Lewis model. Two separate problems are recognized: the first is that of model discrimination, the second that of parameter estimation. It is rare that both problems can be properly treated with a single set of experiments, and we discuss the experimental approaches needed to obtain statistically good results.