| Abstract: | Heterogeneous film‐forming latexes were prepared using two‐stage, seeded emulsion polymerization. The polymerization was performed in a calorimetric reactor with a control unit that monitored the reaction rate and controlled the charging rate of the monomers. Three types of styrene seed latexes were prepared at 70°C. The first was an unmodified polystyrene (PS) latex. The second had the molecular weight lowered by the use of carbon tetrachloride (CCl4) as a chain‐transfer agent, added at the start of the polymerization. For the third one, divinylbenzene (DVB) was used as a comonomer. DVB was added under starved conditions near the end of the polymerization to achieve crosslinked particle shells and to introduce double bonds as possible grafting sites. The second polymerization step was performed at 80°C as a batch operation in a 200‐mL calorimeter reactor. The second‐stage polymer was poly(styrene‐co‐butadiene‐co‐methacrylic acid) (S/B/MAA). A fixed S/B ratio was used together with varying small amounts of MAA. Particle morphology and particle‐size distributions were examined after the second stage using TEM after staining with osmium tetroxide. The particle morphology was found to depend on both the seed composition and the amount of MAA used in the second stage. Molecular weight and crosslinking of the DVB‐containing seed influenced the internal particle viscosity, which gave differences in the polymerization rate and the particle morphology. Crosslinking of the second‐stage polymer decreased the monomer concentration in the particles, which could be detected as a change in the slope the pressure/conversion curve. This phenomenon was used to indicate the critical conversion for crosslinking of the second‐stage polymer. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 297–311, 2000 |
