Acrylonitrile-modified aliphatic amine adducts are often used as curing agents for room-temperature epoxy formulations (coatings, adhesives, sealants, castings, etc.), yet the curing reaction and properties of resultant epoxy systems still remain less fundamentally understood. Herein we systematically investigate our newly-developed acrylonitrile-modified multifunctional polyamine curing agent for bisphenol A epoxy resin (DGEBA): an aciylonitrile-capped poly(propyleneimine) dendrimer (PAN4). The impact of the molecular structure of PAN4 and a controlled poly(propyleneimine) dendrimer (1.0GPPI) on the curing reactivity, reaction mechanisms, thermal stability, viscoelastic response and mechanical properties of the epoxy systems are highlighted. Differential scanning calorimetry (DSC) confirms DGEBA/PAN4 shows markedly lower reactivity and reaction exotherm than DGEBA/1.0GPPI, and the model-free isoconversional kinetic analysis reveals that DGEBA/PAN4 has the generally lower reaction activation energy. To be quantitative, the progress of the isothermal cure is predicted from the dynamic cure by using the Vyazovkin equation. The isothermal kinetic prediction shows that DGEBA/PAN4 requires about 10 times longer time to achieve the same conversion than DGEBA/1.0GPPI, which agrees with the experimentally observed much longer gel time of DGEBA/PAN4. Subsequently, dynamic mechanical analysis shows that PAN4 results in the cured epoxy network with the lower beta- and glass-relaxation temperatures, crosslink density, relaxation activation energy, enthalpy, entropy, but the higher damping near room temperature than 1.0GPPI. Finally, thermogravimetric analysis (TGA) demonstrates cured DGEBA/PAN4 is thermally stable up to 200 degrees C, and mechanical property tests substantiate that PAN4 endows the cured epoxy with much higher impact and adhesion strengths than 1.0GPPI. Our data can provide a deeper insight into acrylonitrile-modified aliphatic amine curing agents from the two good model compounds (PAN4 and 1.0GPPI). (C) 2012 Elsevier B.V. All rights reserved.