Emulsion polymerization of acrylonitrile. Part I. Role and effect of emulsifiers in the emulsion polymerization of acrylonitrile

Abstract

AbstractThe role in and effects on the emulsion polymerization of acrylonitrile (AN) of three different groups of emulsifiers, i.e., low molecular emulsfiers, well‐known water‐soluble polymers, and new water‐soluble polymers containing a sulfonate group have been investigated by a dilatometry and electron microscopy. The major part of this paper concentrates on the study of the relation between the properties of the third group of emulsifiers and emulsion polymerization characteristics of AN such as rate, degree of polymerization, diameter and number of particles, and the degree of dispersion, by adding copolymers of AN and sodium p‐styrenesulfonate (SSS) having various compositions. In the emulsion polymerization of AN, the hydrophobic portion of the emulsifier seems to act as a kind of nucleus around which polymer molecules precipitate and particle formation may occur, and the hydrophilic portion stabilizes the polymer particles thus formed. As the number of particles and the degree of dispersion increases, the total surface of the particles increases, which may raise the overall rate of polymerization due mainly to an increased polymerization on the surface of the polymer particles. The well‐known emulsifiers may be classified by the properties and ratio of the nucleus portion and the stabilizing portion. The unusual effect of emulsifiers on the degree of polymerization may be explained by a chain‐transfer mechanism.