In situ polymerization of N,N-dimethylacrylamide in aerosol OT-water: Modified lamellar structure and multiphase separation

N,N-Dimethylacrylamide is polymerized in the lyotropic surfactant system containing Aerosol-OT (AOT) and water. The polymerization is thermally initiated with AIBN, which allows a homogeneous initiation in this very viscous mixture. The starting mixture contains a lamellar liquid crystalline phase and an isotropic phase in equilibrium. After the polymerization, new phases develop which appear to have a lamellar structure, even if originated from the initial isotropic phase. More phases appear after the polymerization, and they are lamellar, since the phase behavior shifts toward the lamellar region when the monomer is consumed. Once the polymer is formed in situ, it segregates from the lamellae and forms an isotropic microphase which does not macroscopically separate. The appearance of this polymer-rich phase modifies the structure of the lamellar mesophase by partially deswelling it. This gives a shorter lamellar spacing. The law that expresses how the AOT-H2O spacing is contracted by the polymer is deduced from the equilibrium between the two (lamellar and isotropic) microphases. All the macroscopic final phases contain polymer, although in different proportions. The molecular weight of the polymer is the same in all phases. The presence of AOT in the medium has no influence on the resulting tacticity, which is the same as that for a polymer obtained in pure water