Thermosetting polyimides and composites based on highly soluble phenylethynyl-terminated isoimide oligomers

Abstract

Highly soluble phenylethynyl-endcapped isoimide oligomers were synthesized using 2,3,3′,4′-biphenyltetracarboxylic dianhydride (3,4′-BPDA) and aromatic diamines as the monomers, 4-phenylethynyl phthalic anhydride (4-PEPA) as the end-capping reagent, and trifluoroacetic anhydride as the dehydrating agent; then high performance thermosetting polyimides and composites were produced from these oligomers via the thermal crosslinking reaction of the phenylethylnyl group and the material properties were fully investigated. A series of isoimide oligomers with different molecular weights and a variety of chemical architectures were prepared by polycondensation of 3,4′-BPDA, 4-PEPA, and aromatic diamines including m-phenylenediamine (m-PDA), 2,2′-bis(trifluoromethyl)benzidine (TFMB), and 3,4′-oxydianiline (3,4′-ODA), followed by cyclization with trifluoroacetic anhydride. These isoimide oligomers were characterized by means of gel permeation chromatography (GPC), Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), rheological measurements, intrinsic viscosity measurement, and solubility tests. Compared to their imide analogues, isoimide oligomers showed much higher solubility in low boiling point solvents, and slightly lower melt viscosity, which can be attributed to their unique asymmetric architecture. These resins were formulated into thermosetting polyimides and composites by thermal crosslinking of the phenylethynyl group and conversion from isoimide to imide at elevated temperatures. The properties of the thermosets and composites were studied using mechanical property measurements, dynamic mechanical thermal analysis (DMTA), and thermogravimetric analysis (TGA). The cured polyimides exhibited extremely high glass transition temperatures (T_g) up to 467 °C, and 5% weight loss temperatures (T_5%) up to 584 °C in a nitrogen atmosphere. The polyimide/quartz fiber composites possessed excellent high temperature mechanical properties due to the high glass transition temperatures of matrix resins.