Abstract: | Two new pyromellitic dianhydrides, 1,4‐bis(4′‐t‐butylphenyl) pyromellitic dianhydride and 1,4‐bis(4′‐trimethylsilylphenyl) pyromellitic dianhydride, were synthesized via Suzuki coupling, oxidation, and dehydration. A series of new organosoluble polyimides were prepared from the obtained pyromellitic dianhydride and various aromatic diamines by the conventional polycondensation reaction followed by chemical imidization, as well as high‐temperature, one‐step polymerization. The structures of the dianhydrides and polymers were identified with various spectroscopies. The inherent viscosities of the resulting polymers were 0.62–1.89 dL/g. The synthesized polyimides showed good solubility in various organic solvents such as N‐methyl‐2‐pyrrolidinone, N,N‐dimethylacetamide, and p‐chlorophenol. These polymers had glass‐transition temperatures of 230–260 °C. Thermogravimetric analysis showed that all the polymers were stable, with 10% weight losses recorded above 490 °C in nitrogen. The polyimide films had good mechanical properties and high oxygen permselectivity to nitrogen. The oxygen permeability coefficient (P) and the permselectivity of oxygen to nitrogen (P/P) of the films were 13–56 barrer and 3.7–5.5, respectively. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 4288–4296, 2002 |