Abstract
The objective of this PhD thesis is to understand the physico-chemical phenomena that govern the structural and porous properties of ordered mesoporous materials templated by polyion electrostatic complex micelles. It is defended that the sensitivity of the structure to the physico-chemical parameters of the system is due to the water content in the electrostatic complex which is in osmotic equilibrium with the synthesis medium. First, double-hydrophilic block copolymers (DHBC) were synthesized by ATRP controlled polymerization. They form polyion complex (PIC) micelles in the presence of oppositely charged polyelectrolytes such as the neomycin and oligochitosan weak bases. PIC micelles, colloidal analogues to coacervates, were characterized on a large range of concentration and their concomitant progressive compression was observed together with their ordering and finally their transition to lamellar phases. The core structure and composition were studied through the analysis of a model coacervate system, which macroscopically separates and results from complexation between neomycin and sodium polyacrylate. The coacervate contains up to 60 wt.% of water and exhibits the structure of a network of interpenetrated polymers. The water content in the coacervate depends on physicochemical conditions such as pH and concentration of the system, but also on the addition of osmolytes such as alcohol, PEG polymers or simple salts. A series of mesoporous materials were prepared and their structural and porous properties were modulated by simply varying the physicochemical conditions of the synthesis medium, with a unique DHBC/polyelectrolyte pair. Correlations between the volume fraction of the complex core of the mesogenic system and the obtained material structure could be established and it was shown that the contribution of water was highly significant. Increasing the water content in the coacervates induces an increase of the pore size in 2D hexagonal structures or favours the transition towards lamellar phases of lower curvature. As a conclusion, the synthesis of mesoporous materials mediated by the use of electrostatic complex micelles proved to be all the more environment-friendly as it uses water as the main porogen.