Synthesis of hyperbranched polymethylvinylborosiloxanes and modification of addition‐curable silicone with improved thermal stability

This paper reports a non‐catalyzed environmentally friendly method of synthesizing hyperbranched polymethylvinylborosiloxanes (PMVBSs) and their use to improve the thermal stability of normal addition‐curable silicones (ACSs). PMVBSs were synthesized by the direct polycondensation of dimethoxymethylvinylsilane with boric acid at 80–130°C in 1,4‐dioxane or diglyme. They were characterized by gel permeation chromatography; FT‐IR; 1H, 13C, 29Si and 11B NMR; and TGA. PMVBSs were composed of Si―O―Si and Si―O―B bridges with some unreacted B―OH groups remaining, and had a ceramic yield up to 65.97% at 900°C. PMVBS‐modified ACSs (PBS‐ACSs) were prepared by curing the PMVBSs with hydrogen‐containing silicone oil under Karstedt (platinum divinyltetramethyldisiloxane) catalysis. Thermal stability of PBS‐ACSs was characterized by TGA in N2 or air, and ceramic yields as high as 76.7% were obtained. Gas decomposition during the ceramization of PBS‐ACSs was examined by TG/mass spectroscopy. The SiBOC ceramics formed were characterized by FT‐IR, Raman, 29Si and 11B magic angle spinning NMR and elemental analysis. This method provides a valuable way to improve the thermal stability of ACSs.