Chapter 9: Preparation and Self-assembly of Amphiphilic Fluoropolymers

Since the pioneering work on the self-assembly of “crew-cut” amphiphilic block copolymers by Eisenberg's group, the self-assembly of amphiphilic copolymers has attracted significant attention. In the past two decades, a great variety of micro- and nanostructures with different morphologies have been prepared through this bottom-up strategy. Owing to unique solubility or compatibility of fluoropolymers, they are insoluble in water and most organic solvents, and they are also highly incompatible with most hydrocarbon-based hydrophilic and hydrophobic polymers, which make fluoropolymers interesting and special in their self-assembly behavior. This chapter highlights many developments in the synthesis of linear and non-linear fluoropolymers and their self-assembly behaviors in solution. The role of fluorinated segments in determining the self-assembly behaviors and final micellar morphologies is also discussed in detail. Some directions and developments that are likely to emerge from the synthesis and self-assembly of fluoropolymer in the future are also presented.