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.
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.
基金
Funded by the Financial Support of Shanghai Leading Academic Discipline Project(No.B502)
Fundamental Research for the Central University
