Fabrication of Reactive Poly(Phenyl-Substituted Siloxanes/Silsesquioxanes) with Si‒H and Alkoxy Functional Groups via the Piers–Rubinsztajn Reaction

Poly(phenyl-substituted siloxanes/silsesquioxanes) are obtained by the Piers–Rubinsztajn (PR) reaction of hydrogen-containing siloxanes (HCS) with diphenyldialkoxysilanes such as diphenyldimethoxysilane and diphenyldiethoxysilane catalyzed by tris(pentafluorophenyl)borane. (29)Si nuclear magnetic resonance (NMR) spectroscopy, gel permeation chromatography, and refractive index analysis revealed that apart from phenyl substituents and complex structures such as molecular bridges composed of D(2)(Ph2)[(C(6)H(5))(2)Si(OSi)(2)], structures also existed in these polymers, having high refractive indexes (above 1.50) and high molecular weights (75.60 KDa·mol(−1)). As revealed by thermogravimetric analysis, these polymers have high thermal stability as well, with temperature at 5% mass loss (T(5%)) increasing by 182.5 °C and R(w) (residual weight ratio) increasing by 5.17 times from 14.63% to 75.60%, as compared to HCS, exhibiting its potential application as resins for resisting strong heat. Such high-refractive-index and temperature-resistant poly(phenyl-substituted siloxanes/silsesquioxanes) with Si–H and alkoxy functional groups can be used as a good addition-type crosslinking agent with adhesion-promoting properties or a special curing agent that can solidify silicone materials through simultaneous addition and condensation reactions, which has potential application in the light-emitting diode (LED) packaging industry.