[Zurück]

G. Kickelbick:
"Inorganic-Organic Hybrid Materials via the Incorporation of Inorganic Building Blocks into Organic Polymers";
Techn. Universität Wien, Technische Naturwissenschaften und Informatik, 2003.

In the framework of this Habilitation the following major results were obtained:

. The mechanism of the formation of surface-modified metal oxo clusters of the type M_xO_y(OH/OR)_z(OOCR)_w from the mixture of metal alkoxides and functionalized carboxylic acids was clarified. These clusters were incorporated into organic polymers and are therefore important building blocks for functional hybrid materials.

. Surface-modified spherosilicates that can be used as macroinitiators for polymerisation techniques were prepared by the reaction of the octaanion [Si₈O₂₀]^8- with various reactive initiators. It was shown that only a limited number of functional groups could be attached to the rigid inorganic framework via this post-functionalization technique. When initiating groups for controlled radical polymerisations were attached, organic polymers were grafted from the inorganic core in a controlled manner.

. Initiating groups for ATRP were attached by an in situ approach to various metal oxo cluster cores resulting in a high degree of surface-functionalization. The obtained macroinitiators allowed the formation of inorganic-organic core-shell nanoparticles with a good control over the organic polymeric shell.

. Nanocomposites were obtained by polymerisation of surface-functionalized metal oxo clusters with various organic monomers. In these materials the clusters had still their original structure, which was proven by extended X-ray absorption fine structure measurements.

. Novel amphiphilic inorganic-organic diblock copolymers containing a pure polysiloxane backbone with the intention to use them as templates in the synthesis of well-ordered inorganic-organic hybrid materials were synthesized via anionic ring opening polymerisation. The hydrophilic part of the diblock copolymers was tailored via various functionalization reactions.

. The structure of the copper catalyst in ATRP was determined via EXAFS spectroscopy and X-ray single crystal analysis. It was shown that the kind of ligand is important for the formation of the copper complex and its activity. It also influences the Cu-Br bond length, which however, could not be correlated to the rate of deactivation in the catalytic equilibrium.