Dynamic Modeling of Non‐equilibrium Latex Particle Morphology Development During Seeded Emulsion Polymerization

Multiscale Modeling of Branch Length in Butyl Acrylate Solution Polymerization

“…[3,4] Free-radical polymerizations are often modeled using systems of ordinary differential Equations (ODEs), allowing for accurate predictions of certain metrics, such as conversion rate and average molecular weight. These rate-Equation models may also be used to predict spatial variation of properties, as in emulsion polymer particles; [5] however, such models are not well-suited to capture molecular-level details, such as branch length and distance between branches, which may affect bulk properties like viscosity. To gain a more detailed understanding of the branching structure in polymers such as poly(butyl acrylate), a number of modeling approaches have been developed.…”

Monte Carlo Simulation of Emulsion Polymerization Kinetics and the Evolution of Latex Particle Morphology and Polymer Chain Architecture

“…The various reactions occurring in the aqueous phase, which lead to (among other things) entry of radicals into latex particles, are still simulated using ordinary differential equations, as described previously, [15] since the oligoradicals are so short. Here we have assumed that the oligoradicals irreversibly enter the latex particles once they have reached the critical chain length, commonly referred to as the z-mer length.…”

“…Based on these concepts, we have previously developed software [15] to model the radical penetration aspect during seeded emulsion polymerization for the production of composite particles. This program, called UNHLATEX TM KMORPH, simultaneously simulates the kinetics of the polymerization reaction [in order to provide the necessary information (diffusion, propagation, termination rates, etc.)…”

“…This is because the conditions within the latex particle under actual polymerization conditions often combine relatively slow diffusion rates with relatively rapid polymerization rates. Models have begun to appear [11][12][13][14][15] that address these kinetic factors. It has been shown both experimentally [16][17][18][19][20][21] and using mathematical modeling [17][18][19][20][22][23][24][25][26] that one of the major controlling factors in the development of non-equilibrium morphology is the extent to which growing oligomeric radicals can penetrate (by diffusion) into ''seed'' latex particles after entering from the aqueous phase during the second stage polymerization.…”

Controlled/living heterogeneous radical polymerization in supercritical carbon dioxide

“…[117][118][119][120][121][122] The particle morphology is either thermodynamically [123][124][125][126][127] or kinetically [128][129][130][131] controlled-thermodynamic factors favor the morphology with the lowest free energy (as determined by the interfacial tensions between the polymer/polymer phases and the continuous medium/polymers), whereas the kinetically controlled morphology is obtained when kinetic factors prevent the equilibrium morphology from forming. Morphological aspects of CLRP in dispersed systems have recently been reviewed.…”