The glass-rubber and sub-glass relaxation characteristics of ortho-functionalized aromatic polyimides and thermally rearranged polymers were investigated by dynamic mechanical and dielectric methods. Soluble polyimides (HAB-6FDA; APAF-ODPA) were synthesized by chemical and thermal imidization and subject to thermal rearrangement at elevated temperature. For the thermal exposure histories investigated, mass loss studies indicated partial conversion of the polyimide precursor, suggesting the formation of TR copolymers containing both benzoxazole units and residual imide segments. Measurement of storage modulus and loss tangent was used to follow the thermal rearrangement process in-situ as reflected in the suppression of the polyimide glass transition as a function of precursor structure, the nature of the ortho functional groups and prior thermal exposure. In addition, changes in the position and intensity of local relaxations detected across the sub-glass temperature range were correlated with the degree of thermal rearrangement in these polymers. (C) 2012 Elsevier Ltd. All rights reserved.