Amphiphilic Linear-Hyperbranched Block Copolymers with Linear Poly(ethylene oxide) and Hyperbranched Poly(carbosilane) Block

The synthesis of amphiphilic linear-hyperbranched block copolymers with a linear poly(ethylene oxide) (PEO) segment and a hyperbranched poly(carbosilane)s (PCS) block in a rapid three-step strategy is described, combining oxyanionic polymerization with carbosilane chemistry. A linear precursor block copolymer was synthesized via anionic polymerization of allyl glycidyl ether onto a commercial hydroxyl-terminated PEO, using its cesium alkoxide as macro-initiator. The resulting linear AB or ABA-type di- or triblock copolymers serve as polymer cores for the subsequent hydrosilylation polyaddition of an AB2-type carbosilane monomer. Di(allyl)methylsilane or methyldi(undec-10-enylsilane) were em…

Electrocatalytic Properties of Carbosilane‐Based Hyperbranched Polymers Functionalized with Interacting Ferrocenyl Units

Two types of hyperbranched ferrocene-containing polycarbosilanes were obtained by hydrosilylation of polydiallylmethylsilane (hb-PDAMS) and polymethyldiundecenylsilane (hb-PMDUS) with diferrocenylmethylsilane. The redox properties of both polymers have been investigated both in solution and confined onto platinum electrodes. The electrocatalytic activity of polymer-modified electrodes toward the reduction of oxygen as well as the electrochemical reduction and oxidation of hydrogen peroxide has been examined.

Hyperbranched Polycarbosilanes and Polycarbosiloxanes via Hydrosilylation Polymerization

Branched versus linear oligo(dimethylsiloxane): Differences in their thermodynamic interaction with solvents

The thermodynamic behavior of linear and of branched oligo(dimethylsiloxane) (O-DMS) solutions was studied by means of vapor pressure measurements and vapor pressure osmometry at different temperatures for the thermodynamically favorable solvent THF. The branched material required for that purpose was synthesized and afterwards fractionated by means of the single solvent acetone to eliminate components of low degrees of branching. The Flory-Huggins interaction parameters, χ, for the systems THF/O-DMS as a function of composition pass a minimum at all temperatures (25, 40, and 60 °C) in the case of the branched material. For the unbranched oligomer such a minimum is only observed at 60 °C. A…