Kinetic features of the reaction of triethylphosphite with linear halogenmethylated polystyrene

Abstract

The mechanism of Arbuzov's reaction has been studied in great detail and many examples of it have been investigated. Most authors agree with Arbuzov [1] in assuming it to be a two stage reaction [2]. In the first stage the electrophilic reactant is linked to a phosphorus-containing ester to form a quasi-phosphonium type compound; the second stage involves the thermal decomposition of this intermediate compound. A fair number of authors has also dealt with the reaction kinetics, and in spite of some disagreement in regard to the orders and rates of the first and second stages it is generally found in the light of kinetic analysis that the first stage of Arbuzov's reaction is second-order. Differences of opinion exist, however, in respect to the second stage of the reaction [3–7]. Practically every author studying kinetics of Arbuzov's rearrangement and the isomerization kinetics have referred to the great difficulties involved both in the experiments and also in treatment of the kinetic data owing to the complexity of the reaction in question. In recent years reports have appeared on the work of authors using Arbuzov's rearrangement to introduce phosphorus-containing groups into the side chains of different polymers [8–12], but no data have been published regarding the kinetics of Arbuzov's reaction in respect to polymers.