The meta- and para-catenated methylene-containing phthalonitrile oligomers were prepared from the reaction of an excess amount of 4,4′-(4,4′-isopropylidenediphenoxy) bis-(phthalic anhydride) (BPADA) with 4,4′-Methylenedianiline (MDA) in a N, N-dimethylformamide/ toluene solvent mixture, followed by end-capping agent with 4-nitrophthalonitrile or 4-phenoxyaniline in a two-step, one-pot reaction. Differential scanning calorimetry (DSC) showed that both PN oligomers exhibited low softening points. The self-catalyzed curing reactivity of the PN oligomers was confirmed by the isothermal rheological measurements. Fourier transform infrared spectroscopy (FTIR) and ultraviolet and visible spectrophotometry (UV–Vis) data of the pre-curing resins were employed to investigate the chemical structure of the pre-cured resins, suggesting that oligomers generated crosslinking sites, including triazine, isoindoline, and phthalocyanine. The results further confirmed the self-catalyzed curing reactivity of the oligomers. Thermal properties were investigated by dynamic mechanical analysis (DMA) and thermal gravimetric analysis (TGA), demonstrating good thermal properties of the cured resins. The glass transition temperatures (Tgs) of PIPN-1-325, PIPN-1-350, PIPN-1-375 were in the range of 285–345°C, the 5% weight loss temperature (T5%) was observed at 482°C. The PIPN-2-325, PIPN-2-350, PIPN-2-375 showed Tgs ranging from 293 to 370°C, and T5% of the resins were in the range of 481–501°C. Then the isothermal rheological results of model compound and PN oligomers implied that the curing process of PN oligomers was closely related to the methylene-cyano radical thermal synergistic polymerization (TSP) effect proposed in our previous research, and then a revised curing mechanism (radical TSP mechanism) was proposed.
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