| 【文章摘要】 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(~1H-NMR).DSC was adopted to analyze the reactions under bulk polymerization condition,while ~1H-NMR for solution reaction polymerization was conducted.The apparent activation energies(E_α) calculated by Kissinger's method were 77.96,81.24 k J/mol,which were confirmed by Friedman's method,and 65.45,69.36 k J/mol by ~1H-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 ~1H-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. |