| Abstract: | Previous attempts to prepare monodisperse styrene/sodium styrene sulfonate copolymer latexes by batch, seeded, and semicontinuous emulsion polymerization were unsuccessful at high concentrations of the functional comonomer. Broad, and sometimes bimodal, size distributions, and large amounts of water soluble homopolymer were obtained. After removal of free monomer, solute and adsorbed homopolymer and copolymer, the overall incorporation of the functional comonomer was found to be low. To overcome these problems, a two stage “shot-growth” or in situ seeding technique was developed. A first stage copolymerization was carried out with a low concentration of sodium styrene sulfonate: the purpose of the functional comonomer was to enhance the stability and regulate the size of the seed particles. When this reaction had reached high conversion (> 90%), a second stage monomer mixture was added. The ratio of styrene to sodium styrene sulfonate in this mixture determined the final surface charge density. The mechanism by which the NaSS is incorporated in the polymer particles is considered to be by solution copolymerization with solute styrene monomer to form surface active oligoradicals. These radicals adsorb on the particle surface, initiate polymerization and become inextricably bound, preventing their transfer back to the aqueous phase. By this means, it was possible to vary independently the particle size and surface charge density. High concentrations of functional comonomer could be polymerized without undue wastage (incorporations were only slightly less than 100%) or loss of monodispersity. In extreme cases, the area per functional group fell below the theoretical minimum, indicating considerable hydration of the surface layers. |
