Use of poly(styrene)-block-poly(ethyleneoxide) as emulsifier in emulsion polymerization

Summary

Poly(styrene)-block-poly(ethyleneoxide), abbreviated as (PS-b-PEO) were used as emulsifiers in emulsion polymerization of styrene and methyl methacrylate. The block copolymers had a poly(styrene) block with M_n=1000 g/mol and a poly(ethyleneoxide) block with M_n=1000, 3000 or 5000 g/mol, respectively. Stable dispersions were obtained when the PEO block molecular weight was higher than 1000 g/mol. Also the amphiphilic properties of the copolymers depended on the PEO chain length. Block copolymer micelles with hydrodynamic radii between 11 and 17nm were observed. Emulsion polymerization was performed at different block copolymer concentration at 60 and 80°C. Particle size varied between 50 and 300nm and decreased with increasing copolymer concentration. The particle size was larger at higher temperature, but the size distribution was narrower. Polymerization of methyl methacrylate gave smaller particles when compared to styrene. The dispersions were very stable towards high electrolyte concentration, but flocculation occurred at elevated temperatures. Both observations indicate that the dispersions are sterically stabilized.