Association behavior of poly(methyl methacrylate-block-methacrylic acid) in aqueous medium

The atom transfer radical polymerization technique was used to synthesize the poly(methyl methacrylate-block-methacrylic acid) (P(MAA-b-MMA)) copolymer in order to study the aggregation behavior in aqueous solution over the course of neutralization. Combinations of static and dynamic light scattering (SLS, DLS) and potentiometric titration techniques were used to investigate the size and shape of the micelle at various degrees of neutralization (alpha). By comparing the effect of different polymer chain length with similar MMA/MAA ratio on the aggregation behavior during neutralization, we found relatively strong entanglement of long MMA polymer chains. The comparison between the different MMA/MAA ratios showed that longer MMA chains produced more entanglements. Conductometric titration was used to determine the counterion condensation phenomenon during the course of neutralization. At a critical micellar charge density observed at alpha approximately 0.4, Na+ ions are condensed on the polymer chains. The amount of condensed Na+ was evaluated by the conductivity change, yielding the condensation ratio when the polymer was completely neutralized.