Polytriazoles with different structures were prepared by using 4,4'-diazidodiphenylmethane (DAM) with four imide alkynes, DIAH, BPDIA, DIAO, and BADIA, respectively, under the conditions of intrinsic thermal polymerization. And the differences between their polymerization processes and their kinetics were studied by IR and differential scanning calorimetry. The characteristic temperatures were found out through extrapolation, and the relevant kinetics parameters were calculated by Kissinger and Ozawa method. And the effect of the addition of catalyst on the kinetics of the polymerization reaction was also investigated. The results show that the inclusion of flexible structure or the introduction of side group structure in the polymerization system would reduce the initial reaction temperature, peak reaction temperature and activation energy required by the reaction. The reaction level of all four systems is 0.95, which can be considered that the reaction between azide and alkyne is a first-order reaction. And the addition of catalyst to the system can effectively reduce the activation energy required for the reaction. The catalytic effect of different catalysts is obviously different. The reaction activation energy of the system when using Cu(PPh₃)₃Br as catalyst is 138.92 kJ/mol, which has the better catalytic effect.