Pyromellitic dianhydride-based dianhydrides with bulky substituents, such as 1-phenylpyromellitic dianhydride and 1-(4'-trifluoromethylphenyl)pyromellitic dianhydride, were combined with bis(3-aminophenyl)phenylphosphine oxide and 4,4'-phenylene diamine to prepare polyimides with low coefficient of thermal expansion 17 ppm/degrees C) and good adhesion (>100 g/mm). The polyimides were synthesized via a conventional two-step process: preparation of poly(amic-acid) followed by solution imidization with a-dichlorobenzene. The molecular weights of the polyimides were controlled to 25,000 g/mol via off-stoichiometry and the synthesized polyimides were characterized by Fourier transform infrared, nuclear magnetic resonance, differential scanning calorimetry, and thermogravimetric analysis. Their intrinsic viscosity and solubility were also measured, while adhesive property was measured via T-peel test samples of Cu/polyimide. (C) 2010 Wiley Periodicals, Inc. J Apial Polym Sci 117: 736-741, 2010