Incorporation Behavior of Nonionic Emulsifiers inside Particles and Secondary Particle Nucleation during Emulsion Polymerization of Styrene

In previous studies, it was found that a large amount of the polyoxyethylene nonylphenyl ether nonionic emulsifier, Emulgen 911 (E911), was incorporated inside polymer particles obtained at the completion of a conventional emulsion polymerization with potassium persulfate as a typical water-soluble initiator. In this study, to understand the incorporation phenomenon in more detail, the incorporation behavior during a batch emulsion polymerization of styrene was investigated. The percentage of E911 incorporated inside polystyrene (PS) particles relative to the total weight of E911 used in the polymerization increased to 18% until 50% conversion and then decreased and levelled off to 13% at 70-80% conversion. A similar incorporation behavior was observed in a seeded emulsion polymerization of styrene, in which E911 was added to an emulsifier-free PS seed emulsion to set the same E911 concentration as the batch emulsion polymerization before swelling of the PS seed particles with styrene at 70 degrees C for 24 h. These indicate that E911 molecules absorbed once into styrene-swollen PS particles partially exited therefrom into the aqueous medium during the polymerizations. When the E911 concentration in the aqueous medium is kept above the critical micelle concentration for a long period by the repartitioning process of E911 from styrene droplets into styrene-swollen particles via aqueous medium and/or exiting from the styrene-swollen particles into the aqueous medium, secondary particle nucleation continues during the polymerization, resulting in PS particles having a broad size distribution.