Ortho-hydroxypolyimides (HPIs) undergo thermal rearrangement processes in a solid state at high temperatures to produce thermally rearranged polybenzoxazoles (TR-PBOs), which are promising materials for gas separation membranes due to their exceptional permeability-selectivity performance. The strong dependence between the structure of HPIs and the final properties of the TR-PBOs and the high cost of the HPI precursors are considered excellent reasons for their continued study. In this work, a set of low-cost HPIs were synthetized via the reaction of 2,2'-bis(3,4-dicarboxyphenyl)hexalluoropropane dianhydride (6FDA) with 2,4-diaminophenol dihydrochloride (DAP-Cl) and 4,6-diaminoresorcinol dihydrochloride (DAR-Cl). The polyimide made from 6FDA and m-phenylene diamine (MPD) was also obtained for comparison purposes. The polyimide precursors and the corresponding TR-PBOs, which were tested as films, were thoroughly characterized. The glass transition temperature of these precursor polyimides was shown to be a function of the number of hydroxyl groups such that the lowest value corresponded to the polyimide from MPD and the highest value corresponded to that derived from DAR. The conversion rate of HPIs to PBO at different processing temperatures was determined, and the highest conversion rate matched the DAP derived polyimide. With respect to their gas separation properties after thermal treatment at 450 degrees C, these HPIs gave rise to TR-PBOs with very high permeability and satisfactory permselectivity values for several gas pairs. (C) 2015 Elsevier B.V. All rights reserved.