Semicontinuous Emulsion Polymerization of Vinyl Acetate. XI. Influence of Initiator Concentration on Homopolymerization and Copolymerization in the Presence of a Sulfosuccinate Surfactant

In the homopolymerization and copolymerization of vinyl acetate with dibutyl maleate in the presence of the sodium salt of sulfosuccinic acid semiester with nonylphenol ethoxylated with 25 mol ethylene oxide, the initiator, potassium persulfate (KPS), has a higher decomposition rate than in water even after consumption of monomer. The value of the initiator productivity, P, defined as the ratio of the formed polymer over the decomposed KPS, decreases as the batch stage of the semicontinuous process proceeds. The initiator reacts either with free surfactant molecules or with those grafted on poly(vinyl acetate) chains. During the stage of continuous addition of monomers and KPS, a smaller initiator concentration no longer provides proportionality between the added and decomposed amounts of initiator. The increased monomer concentration at the beginning of continuous addition causes the rate of KPS splitting to decrease as most of the surfactant is bound to the surface monomer/polymer particles.