A Linearization Procedure for Determining Radical Reactivity Ratios in Restricted Penultimate Copolymerization Systems, 2

Abstract

A large number of the already published data of the experimental rate constants of propagation as a function of the monomer composition for copolymerization systems has been analyzed by applying a linearization procedure (introduced in the preceding publication) and new linear least square methods in order to obtain the radical reactivity ratios s. The compilation of data comprises the originally published parameter sets and those determined by the alternative methods. Besides the determination of the s parameters, the linearization plots also offer the possibility to rate the error of data sets as either non‐correlated or systematic. Simulations taking into account a random scatter in the experimental values give more insight into the accuracy of data. The limited applicability of the simplifying assumptions introduced by Fukuda et al. is confirmed. Correlations between the monomer and radical reactivity ratios, respectively, and the homopropagation rate constants are investigated. A systematic procedure for rating radical reactivity ratios based on the linearization procedure is proposed.

Compositional gradients in photopolymer films utilizing kinetic driving forces

“…Reactivity ratios are the ratio of the homopolymerization rate constant divided by the copolymerization rate constant giving a simple quantity to examine copolymerization reactivity. 63,64 Moreover, reactivity ratios illustrate which monomer in a copolymerization will preferentially react, the strength of reaction preference, and the behavior of the copolymerization. 22 For instance, the reactivity ratios for a copolymerization of methyl methacrylate and methyl acrylate are 2.2 and 0.4, respectively.…”