Interaction of amphiphilic block copolymer micelles with surfactants

An out line and summary of literature studies on interactions between different types of amphiphilic copolymer micelles with surfactants has been given. This field of research is still emerging and it is difficult presently to make generalisations on the effects of surfactants on the copolymer association.

The effects are found to be varied depending upon the nature and type of hydrophobic (hp) core and molecular architecture of the copolymers and the hydrocarbon chain length and head group of surfactants. The information available on limited studies shows that both anionic and cationic surfactants (in micellar or molecular form) equally interact strongly with the associated and unassociated forms of copolymers.

The beginning of the interaction is typically displayed as critical aggregation concentration (CAC), which lies always below the critical micelle concentration of the respective surfactant. The surfactants first bind to the hydrophobic core of the copolymer micelles followed by their interaction with the hydrophilic (hl) corona parts.

The extent of binding highly depends upon the nature, hydropobicity of the copolymer molecules, length of the hydrocarbon tail and nature of the head group of the surfactant. The micellization of poly(ethylene oxide) (PEO)–poly(propylene oxide) (PPO)–poly(ethylene oxide) was found to be suppressed by the added surfactants and at higher surfactant concentrations, the block copolymer micelles get completely demicellized.

This effect was manifested itself in the melting of liquid crystalline phases in the high copolymer concentrations. However, no such destabilization was found for the micelles of polystyrene (PS)–poly(ethylene oxide) copolymers in water. On the contrary, the presence of micellar bound surfactant associates resulted in to large super micellar aggregates through induced intra micellar interactions.

But with the change in the hydrophobic part from polystyrene to poly(butadiene) (PB) in the copolymer, the added surfactants not only reduced the micellar size but also transformed cylindrical micelles to spherical ones. The mixtures in general exhibited synergistic effects. So varied association responses were noted in the mixed solutions of surfactants and copolymers.