The reaction of poly(allyl azide) (PAA; number-average molecular weight = 1800 g/mol) with N-phenyl maleimide, 4,4'-bis(maleimidodiphenyl) ether, 4,4'-(bismaleimidodiphenyl) sulfone, and 1,6-bismaleimido hexane is described in this article. As indicated by Fourier transform infrared studies, the azido group reacted with the highly electron-deficient olefinic bond of N-phenyl maleimide or bismaleimides in a 3 + 2 cycloaddition reaction under mild reaction conditions. The curing of PAA with bismaleimides (10-30 phr) was monitored with differential scanning calorimetry. In freshly prepared samples of PAA and bismaleimides, a broad exothermic transition was observed in the temperature range of 150-280 degrees C and could be attributed to the loss of N-2 from PAA and the curing of bismaleimides. The heat of the exothermic reaction (Delta H) depended on the structure and composition and was in the range of 800-1413 J/g. Isothermal heating in an air oven at 40 degrees C (2 days) followed by 60 degrees C (5-6 days) resulted in the conversion of a sticky, viscous liquid into an elastic, nonsticky material. No significant difference in the Delta H values of uncured and cured samples was observed, and this indicated the reaction of fewer azido groups with the bismaleimides (dipolarophiles). In the thermogravimetry traces, a mass loss was indicated in the temperature range of 130-280 degrees C due to the loss of nitrogen from the azido group. (c) 2006 Wiley Periodicals, Inc.