Organically modified aluminosilicate mesostructures were synthesized from two metal alkoxides with the use of poly(isoprene-b-ethyleneoxide) block copolymers (PI-b-PEO) as the structure-directing molecules. By increasing the fraction of the inorganic precursors with respect to the polymer, morphologies expected from the phase diagrams of diblock copolymers were obtained. The length scale of the microstructures and the state of alignment were varied using concepts known from the study of block copolymers. These results suggest that the use of higher molecular weight block copolymer mesophases instead of conventional low-molecular weight surfactants may provide a simple, easily controlled pathway for the preparation of various silica-type mesostructures that extends the accessible length scale of these structures by about an order of magnitude.

Endfunctionalized polyisoprenes (PI) and polystyrenes (PS) with either one sulfonate or ammonium end group and α,ω-macrozwitterionic PI and PS have been synthesized and investigated by CW-EPR using the spin probe technique. From the extrema separation of the temperature dependent spectra a characteristic temperature, T‘50G, is introduced which can be employed as a measure for the temperature dependence of the chain end association in these telechelic ionomers. In this way it is shown that the mobility of an ionic 2,2,6,6-tetramethylpiperidine-N-oxyl derivative is dramatically restricted when compared to the corresponding nonionic probe. For PI the reduction in probe mobility corresponds to temperature shifts as high as 140 K relative to the dynamics of the polymer, indicating the presence of highly immobilized ion multiplets. As shown by the temperature dependent data, the method is sensitive to additional immobilization of the ionic domains induced by bulky substituents adjacent to the ionic chain ends. Comparison of the EPR results with structural data from SAXS measurements reveals that the main factors governing the dynamics of multiplets are the chemical type of ionic end group and the nature of the polymer backbone. Analysis of the EPR data for telechelic PS shows that in high-T g polymers the dynamics of the ionic aggregates occurs at comparable time scales as the dynamics of the polymer backbone.

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