An attempt was made to synthesize polyurethane (PU)/organoclay nanocomposite foams with high thermal insulation properties. The organoclay was modified by polymeric 4,4'-diphenylmethane diisocyanate (PMDI) with a Silane Coupling agent. The structure of the organoclay-modified PMDI with the silane coupling agent was determined by Fourier transform infrared spectroscopy and nuclear magnetic resonance. Transmission electron micrographs and wide-angle X-ray diffraction patterns showed that the interlayer distance increased for the PU/organoclay nanocomposites with the addition of the silane coupling agent. It was expected that the distance between the organoclay layers Would increase and that the organoclay would be dispersed on a nanoscale in the PU matrix because of the organic/inorganic hybrid bond formation between the organoclay and silane coupling agent. Compressive and flexural strengths of the PU/silane coupling agent/organoclay nanocomposite foams were similar to those of the PU/organoclay nanocomposite foams. However, the thermal conductivity appreciably decreased from 0.0250 to 0.0230 W/m h degrees C in the PU/silane Coupling agent/organoclay nanocomposite foams. Scanning electron micrographs showed that the cell size of the PU/silane Coupling agent/clay nanocomposite foams also decreased. On the basis of these results, it is suggested that the smaller cell size and lower thermal conductivity of the PU/silane Coupling agent/organoclay nanocomposite foams were mainly due to enhanced exfoliation of the organoclay layers by the silane coupling reaction. (C) 2008 Wiley Periodicals, Inc.