Miniemulsion copolymerizations of styrene (ST) and stearyl methacrylate (SMA) or lauryl methacrylate (LMA) were investigated. Miniemulsions comprising ST and various levels of SMA showed very good storage stability against the diffusional degradation of monomer droplets (Ostwald ripening), whereas miniemulsions comprising ST and various levels of LMA exhibited significant Ostwald ripening. In subsequent miniemulsion copolymerizations of ST and SMA, particle nucleation occurring in the continuous aqueous phase (homogeneous nucleation) plays an important role in the particle formation process in addition to monomer droplet nucleation. The final overall conversion and the individual conversions of ST and SMA all decrease with increasing SMA concentration. Furthermore, at a particular reaction time, the individual conversion of SMA is always greater than that of ST. Monomer droplet nucleation was retarded severely for the monomer pair ST/LMA, presumably due to the very strong Ostwald ripening effect. As a result, relatively slow rates of copolymerization of ST and LMA were attained compared with the ST/SMA counterpart. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011
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