Synthesis and properties of pyrazine-based oligomeric phthalonitrile resins

Abstract

The pyrazine-based oligomeric phthalonitrile (PN) monomer, 2,6-bis[3-(3,4-dicyanophenoxy)phenoxy]pyrazine (BCPP), was synthesized from the reaction of an excess amount of resorcinol with 2,6-dichloropyrazine in the presence of potassium carbonate, followed by end-capping with 4-nitrophthalonitrile in a two-step, one-pot reaction. 4-(Aminophenoxy)phthalonitrile was applied to promote the curing reaction. The curing behavior was investigated by differential scanning calorimetry and rheological behavior, showing a wide processing window of 94°C, a complex viscosity of less than 1.5 Pa·s and a lower reaction activation energy of 32.57 kJ mol−1. The structure of the BCPP monomer was confirmed by Fourier transform infrared spectroscopy and nuclear magnetic resonance spectroscopy. The unit cell was determined to be tetragonal system by wide-angle X-ray diffraction. The monomer was cured to yield cross-linked polymers, which exhibited a high initial storage modulus, excellent glass transition temperature, outstanding thermal stability, and low water uptake.