Abstract: | New phenolic hydroxyl‐pendant aromatic polyimides were synthesized with the N‐silylated diamine method in two steps: the ring‐opening polyaddition of tetrakis(trimethylsilyl)‐substituted 4,4′‐diamino‐3,3′‐dihydroxybiphenyl to various aromatic tetracarboxylic dianhydrides, giving trimethylsiloxy‐pendant poly(amic acid) trimethylsilyl esters, and thermal imidization. The hydroxyl‐bearing polyimides were amorphous but insoluble in organic solvents. They had glass‐transition temperatures greater than 370 °C and temperatures of 10% weight loss greater than 415 °C in nitrogen. The hydroxyl‐pendant polypyromellitimide film had a high tensile strength and a high modulus of 310 MPa and 10 GPa, respectively. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1790–1795, 2002 |