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A series of epoxy vitrimers (EVs) with enhanced glass transition temperatures (Tgs) were synthesized by curing epoxy resin E51 with different ratios of phthalic anhydride and sebacic acid as curing agents, and 1,5,7-triazabicyclic [4.4.0] dece-5-ene as a transesterification catalyst, and their curing dynamics, rheological properties, mechanical properties, and thermal stability were comprehensively investigated. By adjusting the molar ratio of the anhydride to the carboxylic acid in the curing agent, the Tgs of the EVs increased from 79 to 143 °C with the increase in the anhydride content. In particular, the material EV-5.5 with a high usable Tg of 98 °C could undergo stress relaxation through the transesterification reaction when exposed to high temperatures (160 to 200 °C), and the correlation between the relaxation time and temperature follows the Arrhenius equation. Moreover, EV-5.5 exhibited elastomeric behavior, where brittle fractures occurred before yielding, which demonstrated a tensile strength of 52 MPa. EV-5.5 also exhibited good thermal stability with a decomposition temperature (Td5) of 322 °C. This study introduces new possibilities for practical applications of thermoset epoxy resins under special environmental conditions. [ABSTRACT FROM AUTHOR]