Steric Requirements of the Polymer Architecture

Systematic variations of the structural variables characteristic of polymers have been addressed only recently. Most of the work was focused on the role of polymer geometry, as the surfactant fragments with their hydrophilic front part and their hydrophobic back side introduce directionality into the systems [78, 126]. Neglecting polysoaps of the main chain type , isomeric sets of vinylic surfactant monomers were converted into polysoaps of different geometry (Fig. 6), in which the surfactant fragments are fixed at different positions to the backbone (Fig. 8), but which have identical hydrophilic- 

These steric problems with their consequences should affect all vinylic surfactant polymers, independent of the inherent surface curvatures of the different models of polymeric micelles (see Sect. 4.2). Thus, vinylic surfactant homopolymers of other than tail end geometry should be of very limited use as polysoaps. In fact, very few exceptions to the geometry controlled model of solubility have been reported [82, 106, 128, 225, 289-291]. In these examples, the chemical integrity of the polymers prepared, the attributed structures, or the polymeric nature may be questioned considering the results obtained for very similar compounds [115,232,309], But even if these exceptions are real, this rule will help to design new monomers and polymers. 

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