"Click" chemistry is a frequently used technique in polymer chemistry for coupling polymer end groups to construct novel copolymer architectures and as a step-growth polymerization technique. In this study, the bulk polymerization of a diyne and a bisazide were achieved through the copper-catalyzed alkyne-azide 1,3-cycloaddition (CuAAC) with different catalysts, including the homogeneous catalyst Cu(PPh3)(3)Br and a heterogeneous Cu/C catalyst. The effects of different catalyst systems on the kinetics of the "click" polymerization were evaluated by differential scanning calorimetry (DSC) and oscillatory rheology. Additionally, the thermomechanical properties of resulting polymers were evaluated by temperature-ramp oscillatory rheology and thermal stabilities by thermogravimetry. (C) 2011 Elsevier Ltd. All rights reserved.