ABSTRACT
Examples of polymeric amphiphiles include diblock copolymers and proteins. These two examples represent the two poles of this family, the simplest and the most complex. Intermediate cases include, among others, block copolymers of various architectures, graft or comb copolymers, and polysoaps. The aim of this chapter is to present a didactic, though incomplete, theoretical viewpoint of polymeric amphiphiles. In particular, we address two questions: what are the features that distinguish polymeric surfactants from monomeric, low molecular weight, amphiphiles and how is the behavior of polymeric amphiphiles related to their molecular architecture? As we discuss, some broad features are common to monomeric and polymeric surfactants. Both self-assemble into supramolecular structures such as micelles, lamellae, etc. In turn, these supramolecular aggregates can form ordered mesophases. However, the polymeric surfactants do exhibit qualitatively distinctive features with respect to their monomeric counterparts. These include the formation of physical gels and of distinctively polymeric mesophases. Certain polymeric amphiphiles can also undergo intrachain self-assembly that affects their configurations and elasticity. In any case, the underlying physics that controls the size and the shape of the self-assembled structures are significantly modified.
