Abstract: | Novel bismaleimide‐modified siliconized epoxy intercrosslinked network systems were developed. Siliconized epoxy systems containing 5, 10, and 15% siloxane units were prepared using epoxy resin and hydroxyl‐terminated polydimethylsiloxane (HTPDMS) with γ‐aminopropyltriethoxysilane (γ‐APS) as a compatibilizer and dibutyltindilaurate as a catalyst. The siliconized epoxy systems were further modified with 5, 10, and 15% (wt %) of bismaleimide [(N,N′‐bismaleimido‐4,4′‐diphenylmethane) (BMI)] and cured by diaminodiphenylmethane (DDM). Differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and heat‐distortion temperature measurement of the matrix samples were carried out to assess their thermal behavior. DSC thermograms of the BMI‐modified epoxy systems show unimodel reaction exotherms. The glass transition temperature (Tg) of the cured BMI‐modified epoxy and siliconized epoxy systems increases with increasing BMI content. Thermogravimetric analysis and heat‐distortion temperature measurements indicate that the thermal degradation temperature and heat‐distortion temperature of the BMI‐modified epoxy and siliconized epoxy systems increase with increasing BMI content. The morphology of the BMI‐modified siliconized epoxy systems was also studied by scanning electron microscopy (SEM). © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 2330–2346, 2001 |