Polymeric vs. monomeric amphiphiles: Design parameters

The distinctive features of polymeric surfactants as compared to monomeric, low molecular amphiphiles are reviewed from a theoretical point of view. The relative importance of the configurational entropy is discussed and illustrated for polymeric micelles formed from three different types of diblock copolymers. When the number of amphiphilic motifs within the polymer increases, distinctively polymeric features appear. Bridging and exchange interactions play an important role when the number of blocks is three and above. This gives rise to the formation of physical gels. Intrachain self-assembly occurs in multiblock copolymers and polysoaps and affects the configurations, dimensions and elasticity of the single chain.