Several zwitterionic polymers were prepared by radical homopolymerization of surfactant monomers which bear diallyl, diene or vinylcyclopropane moieties. These polymer systems were complemented by alternating copolymers of appropriate zwitterionic vinyl compounds. Thus, polymers with reduced (as compared with simple vinylic homopolymers, or statistical copolymers) and well defined density of surfactant side groups are obtained. The solubilities found for these polymers are dominated by polymer geometry rather than by the balance of hydrophilic and hydrophobic fragments, thus corroborating a “main-chain spacer” model proposed recently. All water-soluble polymers exhibit characteristic featur…

Structure and properties of zwitterionic polysoaps: functionalization by redox-switchable moieties

Redoxactive monomeric and polymeric surfactants containing viologen and N-alkylated nicotinic acid moieties were synthesized. These systems are potentially able to trigger reversible changes of self-organization by creation or removal of a charge via a redox reaction. Hence, they are investigated with respect to solubility, aggregation behavior, and their electrochemical properties in water. — All monomers, but only the viologen polymers are water-soluble and drastically decrease the surface tension of water. Critical micelle concentrations are observed for the monomers only. — The chemical reversibility of the redox reactions of the compounds in water was investigated using cyclic voltamme…

Recent achievements in the field of micellar polymers, or «polysoaps» are described. Taking advantage of zwitterionic model polymers, systematic variations of the molecular architecture have provided an improved understanding of the relationship between the molecular structure of the polymers and their key properties such as surface activity and solubilization capacity. Useful rules are established, which take into account much of the previous data in the literature

Solubilization control by redox-switching of polysoaps

Reversible changes in the self-organization of polysoaps may be induced by controlling their charge numbers via covalently bound redox moieties. This is illustrated with two viologen polysoaps, which in response to an electrochemical stimulus, change their solubility and aggregation in water, leading from homogeneously dissolved and aggregated molecules to collapsed ones and vice verse. Using the electrochemical quartz crystal microbalance (EQCM), it could be shown that the reversibility of this process is better than 95% in 16 cycles.

Preparation des polymeres (CHR-CH 2 SO 2 ) (R=(CH 2 ) 9 N + Me 2 (CH 2 ) 3 SO 3 − , (CH 2 ) 8 CO[NC 4 H 8 N + (Me)([CH 2 ] 3 SO 3 − )] et R=CH 2 OCH 2 CHOHCH 2 N + Me(C 10 H 21 )(CH 2 ) 3 SO 3 − ) par copolymerisation spontanee des sels d'ammonium vinyliques correspondants avec SO 2 dans l'eau. Leurs proprietes de surface et de solubilisation de molecules hydrophobes en solution aqueuse sont caracteristiques de polysavons

Solubilization by polysoaps

The aqueous solubilization power of several series of micellar homopolymers and copolymers (''polysoaps'') is investigated. Using five insoluble or poorly water-soluble dyes, comparisons of the capacities are made with respect to the influence of structural variables such as the polymer backbone, the polymer geometry, the comonomer content, and the charge of the hydrophilic group. Some guidelines for polysoap structures suited for efficient solubilization are established. Noteworthy is that the solubilization capacities of the polysoaps are neither linked to the ability to reduce the surface tension of water, nor to the polarity of the solubilization sites deduced from spectroscopic probes.