Journal of Applied Polymer Science, Vol.77, No.2, 297-311, 2000
Influence of seed polymer molecular weight on polymerization kinetics and particle morphology of structured styrene-butadiene latexes
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 degrees C. The first was an unmodified polystyrene IFS) 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 degrees 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 nifh 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.
Keywords:two-stage;seeded emulsion polymerization;calorimetric reactor;particle viscosity;monomer vapor pressure;particle morphology;core-shell