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Stable Free Radical Polymerization in Emulsion: Modeling the Thermodynamics of Monomer Transfer between Droplets and Particles
Author(s) -
Pohn Jordan,
Buragina Catherine,
Georges Michael K.,
Keoshkerian Barkev,
Cunningham M. F.
Publication year - 2008
Publication title -
macromolecular theory and simulations
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.37
H-Index - 56
eISSN - 1521-3919
pISSN - 1022-1344
DOI - 10.1002/mats.200700060
Subject(s) - emulsion polymerization , polymerization , monomer , polymer , kinetics , radical polymerization , particle (ecology) , polymer chemistry , chain transfer , styrene , chemistry , kinetic chain length , materials science , thermodynamics , chemical engineering , copolymer , organic chemistry , physics , oceanography , quantum mechanics , engineering , geology
A mathematical model is developed from polymer solution thermodynamics and stable free radical polymerization kinetics to predict the monomer swelling behavior of large droplets and small particles that coexist during the seeded polymerization of styrene in emulsion. This model is used to predict the sensitivity of polymerized latex stability (based on the persistence of large particles) to changes in seed particle size and final latex target molecular weight. Simulation results show that the use of small seed particles (diameter ≤ 50 nm) in recipe formulation will lead to polymerization occurring preferentially in the large droplets, and offers theoretical evidence that TEMPO‐mediated ab initio emulsion polymerizations will not be feasible. Our predictions are consistent with experimental evidence suggesting that the presence of large particles leads to the formation of undesirable coagulum in the final product.