Hyperbranched Polyalkoxysiloxanes via AB3‐Type Monomers

We have synthesized polyethoxysiloxanes starting from the AB3‐type monomers triethoxysilanol and acetoxytriethoxysilane. The polymers are liquid and soluble in organic solvents.29Si NMR spectroscopy and MALDI‐ToF mass spectrometry analyses show that the polymers have a hyperbranched structure with additional internal cyclization.29Si NMR spectroscopy indicates that the polymer synthesized from acetoxytriethoxysilane is less branched than the polymer synthesized from triethoxysilanol. Analysis of the molar mass and mass distribution of the polymers via size exclusion chromatography (calibrated via MALDI‐ToF MS and viscosimetry) yields a molar mass ofMn ≈ 2 kg · mol−1andMw ≈ 8 kg · mol−1for polymers synthesized from triethoxysilanol. The molar mass of the polymers synthesized from acetoxytriethoxysilane can be controlled by variation of the polymerization time in the range ofMn ≈ 1.8–12 kg · mol−1andMw ≈ 2.1–2 200 kg · mol−1. Photograph of a vial containing polyethoxysiloxane obtained from triethoxysilanol and a schematic drawing of the proposed molecular structure of the polymer. magnified image Photograph of a vial containing polyethoxysiloxane obtained from triethoxysilanol and a schematic drawing of the proposed molecular structure of the polymer.