Kinetic effects of surfactants on a polymer reaction in a nonaqueous system: Nucleophilic substitution of poly(vinyl chloride) with the azide ion

Abstract

AbstractCationic surfactants such as laurylpyridinium chloride and tetrabutylammonium chloride catalyze the nucleophilic substitution of poly(vinyl chloride) with sodium azide in tetrahydrofuran, dioxane and cyclohexanone in which sodium azide is insoluble. An anionic surfactant, sodium laurylbenzenesulfonate, does not catalyze the reaction. It was assumed that a quarternary cation exchanges a chloride ion for an azide ion and then transfers it to the reaction site of poly(vinyl chloride) through the solvent. The reaction of poly(vinyl chloride) with laurylpyridinium azide was also investigated, and a saturation phenomenon in the relationship between the rates and the concentrations of laurylpyridinium azide was observed. The kinetic data are discussed in terms of an “adsorption” of the quarternary salts on a poly(vinyl chloride) chain.