Effects of poly(acrylic acid) electrosteric stabilizer on entry and exit in emulsion polymerization

A methodology developed to obtain rate coefficients for entry and exit (desorption) in emulsion polymerizations was applied to systems stabilized electrosterically by a copolymer of acrylic acid and styrene embedded in a styrene seed particle. This was grown as a second-stage procedure, by adding styrene and acrylic acid to a styrene seed and then polymerizing. Rate coefficients for entry (ρ) and exit (k ) for subsequent homopolymerization of the resulting latices with styrene were obtained from the time dependence of the approach to steady state using both chemical and γ-radiolytic initiation; the latter was used in relaxation mode, which measures k directly. Compared to the same latices with an electrostatic stabilizer, at pH 7 the electrosteric stabilizer greatly reduced both ρ and k. When ionic strength was increased, ρ increased relative to that found for electrosterically stabilized latex in the absence of added electrolyte. For electrostatically-stabilized latices, entry is supposed to occur by aqueous-phase propagation to a critical degree of polymerization z which then undergoes irreversible entry; the present data for electrostatically-stabilized latices support this model, including its prediction that ρ be independent of particle size, all other things being equal. The decrease in ρ in the electrosterically-stabilized latices is ascribed to a "hairy" layer through which diffusion of a z-mer is slow, so that it may be terminated prior to actual entry. For electrostatically-stabilized latices, exit is supposed to occur by transfer, resulting in a monomeric radical which exits by diffusing through the aqueous phase, this event competing with intraparticle propagation; the decrease k in the electrosterically-stabilized latices (also seen in other polymerically-stabilized systems) can be interpreted by assuming that aqueous-phase diffusion slower in the hairy layer.