Polymerization of methyl methacrylate in 3‐component cationic microemulsion

Methyl methacrylate has been polymerized in three‐component o/w microemulsions made with the cationic surfactant dodecyltrimethylammonium bromide (DTAB). The effects of temperature type and concentration of initiator (AIBN or potassium persulfate), and surfactant and monomer concentration on polymerization kinetics are investigated. Final conversions and reaction rates increase with increasing monomer and initiator concentrations and with higher reaction temperatures. The rate of polymerization shows initiation and termination intervals, but no constant rate interval is observed. Both molecular weight and particle size decrease as the concentration of initiator increases, regardless of type of initiator. Latexes with small particle size (< 70 nm) and high molecular weights (>106) were obtained in all cases. Activation energies for the microemulsion polymerization of MMA with AIBN (10.3 kcal/mol) and KPS (13.4 kcal/mol) are smaller than that of bulk polymerization using AIBN (20 kcal/mol).