Cationic ionenes bearing hydrophobic side chains were synthesized, which behave as micellar polymers of the polysoap type. The hydrophobic chains were either hydrocarbons or fluorocarbons, or a mixture of both, in the form of statistical as well as block copolymers. These amphiphilic polymers were studied and compared with each other and with low molar mass analogous surfactants, especially with respect to their hydrophobic association in aqueous solution. The particular molecular structure of the ionenes synthesized results in polymeric surfactants with high mobility of the fluorocarbon chains. Most noteworthy, the behavior of the hydrocarbon-fluorocarbon block copolymer soaps in aqueous solution indicates microphase separation into hydrocarbon-rich and fluorocarbon-rich hydrophobic domains, thus yielding multicompartment micelles.

Cationic polymerizable surfactants based on styrene with fluorocarbon chains and their hydrocarbon analogues were synthesized, and copolymerized to give micellar polymers of the polysoap type. Characteristically, the fluorocarbon polymers show a higher tendency for self‐organization, but also much less mobile hydrophobic associations in aqueous media than their hydrocarbon counterparts. In contrast to statistical terpolymers of similar average composition, block copolymers made of a fluorocarbon polysoap block and a hydrocarbon polysoap block via the radical addition fragmentation chain transfer (RAFT) method give rise to not only microphase separation between the hydrophilic polar parts and the hydrophobic apolar parts of the macromolecules, but also seem to be able to undergo additional microphase separation between hydrophobic domains made of fluorocarbon chains and those made of hydrocarbon chains, at least in the solid state.

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Two amphiphilic AB block copolymers, containing a highly compatible poly(epsilon-caprolactone) (PCL) block connected to a poly(dimethylsiloxane) (PDMS) block having a low surface energy, are synthesized and characterized in terms of their dispersion in a presynthesized PCL matrix. X-ray photoelectron spectroscopy, contact angle measurements, atomic force microscopy, and optical microscopy are used to describe the evolution of the surface chemical composition, as well as the surface and bulk morphology of the PCL/copolymer blends as a function of the nature and weight surface free energy and the dispersion of the copolymers in the blends, leading to important modifications of the bulk and the surface morphology. These differences are interpreted in terms of the impact of the block copolymers on the semicrystalline polymer structure and related properties in the prospect of using the surfactants to improve the synthesis of PCL in supercritical CO(2).