Colloidal dispersions of nanometer sized palladium colloids with very high stability were prepared in block copolymer micelles of polystyrene-b-poly-4-vinylpyridine and analyzed by electron microscopy and X-ray analysis. The resulting polymer/metal hybrids can easily be dissolved and handled in standard organic solvents such as toluene, tetrahydrofuran, and cyclohexane. They were successfully used for the Pd-catalyzed carboncarbon coupling of aryl halides with alkenes (Heck reaction). Such block copolymer stabilized palladium colloids exhibit about the same reactivity as low molecular weight Pd complexes classically used for the Heck reaction, but show a much higher stability: in most reactions, the hybrids remain catalytically active even after 50000 turn-over cycles. Reaction rates were significantly controlled by the reactivity of the educts, but also respond to micelle architecture and dispersity of the palladium. Other advantages of the block copolymer stabilizer are that they are more simple and readily accessible than the phosphor-containing chelates, and that they dissolve even in "simple" solvents such as toluene (instead of amidic solvents).

A variety of amphiphilic blockcopolymers (ABC's) are made by using two highly effective polymer analogous reactions, epoxidation followed by opening of the oxirane ring. The optimization of all reaction conditions results in functional polymers which are practically as narrowly distributed as their precursor polymers, and which can be used as model polymers. In case of polar modification, all amphiphilic block copolymers form well-defined micelles in toluene, the size of which can be adjusted by the type of modification. The adjustment of the amphiphilicity with diverse nitrogen, sulfur, and phosphonate derivatives results in polymeric amphiphiles with a high affinity to transition metal ions, as well as metal colloids and surfaces. This is demonstrated by solubilization of metal salts in unpolar solvents by the ABC's and subsequent formation of well-defined noble metal colloids which arein the case of a careful adaption of the polymer to the metal surfaceperfectly stabilized by the corona polymers.

Block copolymers consisting of polystyrene and a block containing long fluorinated side chains are made by two very effective polymer analogous reactions from commercially available polystyrene-b-polybutadiene block copolymers. Since these polymers consist of two mutually immiscible blocks with hydrophobic and very hydrophobic character they form micelles in a wide range of media down to very hydrophobic solvents, e. g. toluene, tetrahydrofurane (TI-IF), peffluorohexane, perfluoro(methylcyclohexane), hexafluorobenzene and 1,1,2-trichlorotrifluoroethane (Freon 113). First indications that our polymers are useful as effective steric stabilizers in such solvents are given by characterization of some polymer dispersions made in these solvents via precipitation polymerization. In the solid state, mesophase formation typical for block copolymers is observed and characterized by quantitative small angle X-ray scattering (SAXS). The surface of such films is controlled by the fluorinated Mock and exhibits an ultra-low surface energy of the order of ysv = 15 mN/m, below that of polytetrafluoroethylene (PTFE) or polydimethylsiloxanes (PDMS). Unlike PTFE, the blocky nature of the presented polymer enables thermoplastic processing and dissolution in standard solvents, which is of practical relevance. Gas-permeability measurements on membranes coated with these copolymers exhibit some interesting selectivities. Acta Polymer., 48, 262-268 Q VCH Verlagsgesellschaft mbH, D-69451 Weinheim 1997

Amphiphilic block copolymers made by a variety of techniques form in selective solvents micelles of well defined size and shape. We report on the underlying principles of micelle formation, as revealed by light scattering experiments.In addition, we will delineate some applications of these block‐copolymer micelles where we focus on two technological relevant cases, namely the stabilization of polymer particles in low cohesion energy environments as well as the stabilization of metal and semiconductor colloids inside specially functionalized block copolymer micelles. In the latter case, stable hybride materials are obtained where the properties both of the polymer and the inorganic are added in a synergistic way. First data on special catalytic properties, the generation of superparamagnetic materials, and special colloids with optical functionality are presented.

Block copolymers made of polystyrene and fluorinated blocks represent a new class of polymers with a very strong incompatibility between the two blocks. They exhibit new stable block copolymer mesophases which are not considered in the phase diagrams of diblock copolymers in the strong and super-strong segregation regime. The solid-state structures of two polymers with different compositions are characterized by synchrotron small-angle X-ray scattering and transmission electron microscopy, thus proving the existence of a quadratically perforated layer phase and a 2D phase of sanidically degenerated cylinders.