Organic-inorganic hybrid materials with a high thermal stability and a low dielectric constant show great potential in the microelectronics industry. In this work, polyhedral oligomeric silsesquioxane-benzocyclobutenes (POSS-BCBs) were synthesized by a hydrosilylation reaction of octavinyloctasilasesquioxane (OVPOSS) and 4-(1,1-dimethyl-1-hydro)-silyl-benzocyclobutene with H2PtCl6 as a catalyst. The ring-opening reaction of BCB on POSS-BCBs resulted in POSS-BCB resins with a highly cross-linked network structure. This resin exhibited good thermal stability (T5% is 495°C in N2), low dielectric constants (<2.1 at 20 MHz) and low water absorption.

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A new single-phased thermosetting resin (propargyloligosilazane, POSZ) was prepared through Hofmann alkylation of oligosilazane with propargylbromide; the propargyl content in POSZ was controlled by monitoring the amount of propargylbromide in synthesis. The characterizations showed that POSZ has ideal rheology during material processing, the thermal curing temperature could be lowered when isocyanate was used as crosslinking agent, and the thermally cured POSZ can be pyrolyzed into anti-oxidative ceramic at a high yield of >70%. For POSZ-matrixed carbon-fabric laminate composite, it possessed high mechanical properties and retained the original shape with the increase of temperature as high as 800 °C. The POSZ-matrixed laminate has the mechanical properties combining polymer character at room temperature and ceramic character at high temperature, and it will find many prospective high temperature applications in need of polymer and ceramic properties simultaneously.

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