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Journal of Polymer Science Part A: Polymer Chemistry, Vol.35, No.2, 385-390, 1997
Synthesis and Thermochemistry of Phenylmaleimide-Terminated and Phenylnadimide-Terminated Bisphenol-A Polycarbonates
Phenylmaleimide (PMI)- and phenylnadimide (PNI)-terminated bisphenol A polycarbonates (PCs) were prepared by solution or interfacial phosgenation processes, and their thermal crosslinking, both with and without a free radical initiator, and the thermal stability of the resultant network polymers were investigated. m-PMI PCs were prepared by interfacial phosgenation of bisphenol A and m-hydroxyphenylmaleimide, but p-hydroxyphenylmaleimide caused rapid phosgene hydrolysis under interfacial conditions and PCs from it could only be made by solution phosgenation. The degree of crosslinking of PMI PCs, as measured by their gel fraction, heated in the absence of a free radical initiator was generally higher at 250 degrees C than at 300 degrees C and increased with the concentration of PMI end groups. m- and p-PMI PCs form thermosets having nearly complete gel fractions by radical initiated curing at 150-200 degrees C. The gel fraction of these thermosets decreases with exposure to higher temperatures (300 degrees C). This behavior is attributed to BA PC chain degradation induced by nitrogen-containing maleimide reaction products. p-PNI PC was prepared by solution phosgenation and the thermal reaction of it in the presence of the initiator produced only a small increase in molecular weight.