Effect of the presence of polymer in miniemulsion droplets on the kinetics of polymerization

• Published in: Journal of polymer science. Part A, Polymer chemistry Polymer chemistry, 1994-09, Vol.32 (12), p.2365-2376
• Main Authors: Miller, C. M., Blythe, P. J., Sudol, E. D., Silebi, C. A., El-Aasser, M. S.
• Format: Article
• Language: English
• Subjects: Applied sciences; Exact sciences and technology; kinetics; latex particles via nucleation in droplets; miniemulsion polymerization; miniemulsion polymerization, kinetics; Organic polymers; Physicochemistry of polymers; Polymerization; Preparation, kinetics, thermodynamics, mechanism and catalysts; reactor calorimeter; reactor calorimeter, miniemulsion polymerization; styrene/polystyrene; styrene/polystyrene, miniemulsion polymerization
• ISSN: 0887-624X; 1099-0518
• DOI: 10.1002/pola.1994.080321217

Solution of polystyrene in styrene were dispersed in an aqueous gel phase comprising sodium lauryl sulfate, cetyl alcohol, and water using an emulsification process known to produce monomer droplet sizes inthe submicron size range (referred to as miniemulsion droplets). The shelf‐life stabilities of these miniemulsions were studied to determine their relative droplet sizes, and the emulsions were concommitantly polymerized in an isothermal batch reaction calorimeter. The polymerization kinetics and final particle sizes produced were compared with miniemulsion and conventional emulsion polymerizations prepared using equivalent recipes without the addition of polystyrene. The results indicate that polymerization of miniemulsions prepared from polymer solutions produce significantly different kinetics than both miniemulsion and conventional emulsion polymerizations. In general, a small amount of polymer greatly increases the rate of polymerization and the final number of particles produced in the polymerization to the extent where even conventional polymerizations carried out above the critical micelle concentration of the surfactant polymerize more slowly. The results are explained by considering the system to be comprised of small, stable pre‐formed monomer‐swollen polymer particles which are able to efficiently capture aqueous phase radicals. This enables the system to produce a large final number of particles, similar to the initial number of pre‐formed polymer particles, as opposed to miniemulsions and micelles in which only a relatively small fraction of the initial number of species (droplets or micelles) become polymer particles. © 1994 John Wiley & Sons, Inc.