High-Tg Polyimide Matrix Composites via Backbone Ethynyl Crosslinking: Preparation and Short-Term High-Temperature Performance

Carbon fiber-reinforced polyimide composites are critical for aerospace applications in high-temperature environments of 300–500 °C. However, conventional PMR-15- and PEPA-terminated polyimides are limited by their insufficient glass transition temperatures (Tg) and low crosslinking densities. This study proposes a reactive backbone construction strategy by employing 4,4′-(ethyne-1,2-diyl)diphthalic anhydride (EBPA) as a difunctional monomer copolymerized with asymmetric 2,3,3′,4′-biphenyl tetracarboxylic dianhydride (α-BPDA) and 4,4′-oxydianiline to synthesize polyimide resins containing both backbone ethynyl and terminal phenylethynyl groups. The effects of EBPA content on the curing behavior, thermomechanical properties, and elevated temperature mechanical performance were systematically investigated. The incorporation of EBPA significantly elevated Tg from 378 °C to 486 °C. Compared to the EBPA-0 control, the optimized EBPA-2 composite exhibited 7.3% and 3.6% improvements in room temperature flexural strength and modulus, respectively. Notably, at 400 °C, EBPA-2 demonstrated retention rates of 69.9%, 93.7%, and 61.6% for flexural strength, flexural modulus, and interlaminar shear strength, exceeding EBPA-0 by 16.9, 8.9, and 18.6 percentage points. SEM analysis confirmed the effective suppression of interfacial debonding at elevated temperatures. These findings elucidate the structure–property relationships between molecular structure, Tg, and short-term high-temperature mechanical retention, providing a promising resin matrix for advanced aerospace carbon fiber composites.