Dumbbell‐Shaped, Graft and Bottlebrush Polymers with All‐Siloxane Nature: Synthetic Methodology, Thermal, and Rheological Behavior

A methodology for synthesizing a wide range of dumbbell-shaped, graft and bottlebrush polymers with all-siloxane nature (without carbosilane linkers) is suggested. These macroarchitectures are synthesized from SiOH-containing compounds—silanol (Et3SiOH) and siloxanol dendrons of the first and second generations, with various peripheral substituents (Me or Et)—and from linear siloxanes comprising terminal and internal SiH groups by the Piers–Rubinsztajn reaction. Products and key building blocks are obtained in yields up to 95%. These polymers are heat and frost-resistant siloxanes. As it turns out, the product physical properties are determined not only by the macromolecular structure, the linear chain length, the size and frequency of branched pendant, but also by the type of peripheral substituents—Me or Et—in the pendant. Thus, the viscosity of the graft polymers with branched pendant groups comprising peripheral Me-groups is more than ≈3–5 fold lower than that of analogous polymers with peripheral Et-groups.