The E-beam curable BMI resin systems and phenylethynyl terminated AFR-PEPA-4 oligomer together with an imide model compound N-phenyl-[4-(phenylethynyl) phthalimide] were synthesized and characterized. E-beam exposure cannot propagate the polymerization of BMI system until the temperature goes up to 100oC. However, a small amount of oligomers may be generated from solid-state cure reaction under low E-beam intensity radiation. Higher intensity E-beam at 40 kGy per pass can give above 75% reaction conversion of BMI with thermal cure mechanism involved. NVP is a good reactive diluent for BMI resin. The cure extents of BMI/NVP increase with the increase of the dosage and applied dosage per pass. The reaction rate is much higher at the beginning of the E-beam cure and slows down after 2 dose passes due to diffusion control. Free radical initiator dicumyl peroxide can accelerate the reaction rate at the beginning of E-beam cure reaction but doesnA?t affect final cure conversion very much. According to the results from FT-IR, 200 kGy total dosage E- beam exposure at 10 kGy per pass can give 70% reaction conversion of BMI/NVP with the temperature rise no more than 50oC. The product has a Tg of 180oC. The predicted ultimate Tg of cured AFR-PEPA-4 polyimide is found to be 437.2oC by simulation of DSC Tg as a function of cure. The activation energy of thermal cure reaction of AFR-PEPA-4 oligomer is 142.6 A+- 10.0 kJ/mol with the kinetic order of 1 when the reaction conversion is less than 80%. The kinetics analysis of the thermal cure of N-phenyl-[4-(phenylethynyl) phthalimide] was determined by FT-IR spectroscopy by following the absorbance of the phenylethynyl triple bond and conjugated bonds. The thermal crosslinking of N-phenyl-[4-(phenylethynyl) phthalimide] through phenylethynyl addition reaction has a reaction order of 0.95 and an activation energy of 173.5 A+- 8.2 kJ/mol. The conjugated bond addition reactions have a lower reaction order of 0.94 and lower activation energy (102.7 A+- 15.9 kJ/mol). The cure reaction of N-phenyl-[4-(phenylethynyl) phthalimide] can be described as a fast first-order reaction stage followed by a slow second stage that is kinetically controlled by diffusion.
