Kinetic study of thermal polymerization reactions between diazide and different diynes

The reaction kinetics between diazide(4,4’-biphenyl dibenzyl azide) and different diynes (dipropargyl bisphenol A and 1,3-diethynylbenzene) were studied by means of differential scanning calorimetry (DSC) and nuclear magnetic resonance spectroscopy ( 1 H-NMR). DSC was adopted to analyze the reactions under bulk polymerization condition, while 1 H-NMR for solution reaction polymerization was conducted. The apparent activation energies ( E α ) calculated by Kissinger’s method were 77.96, 81.24 kJ/mol, which were confirmed by Friedman’s method, and 65.45, 69.36 kJ/mol by 1 H-NMR for dispropargyl bisphenol A/4,4’-biphenyl dibenzyl azide and 1,3-diethynylbenzene/4,4’-biphenyl dibenzyl azide, respectively. The polymerizations between the diazide and diynes were first-order reactions based on calculation from both DSC and 1 H-NMR. The results showed that the reaction between dipropargyl bisphenol A and 4,4’-biphenyl dibenzyl azide was easier than that between 1,3-diethynylbenzene and 4,4’-biphenyl dibenzyl azide, verifying that the reactivity of aliphatic alkyne was higher than that of aromatic alkyne.