A highly efficient and selective[2+2+2]cyclization of diynes and monoalkynes was catalyzed by rhodium under room temperature in water/THF mixed solvent,affording isoindolines and isobenzofurans in good to excellent yi...A highly efficient and selective[2+2+2]cyclization of diynes and monoalkynes was catalyzed by rhodium under room temperature in water/THF mixed solvent,affording isoindolines and isobenzofurans in good to excellent yields.The center atoms (N,O) in the diynes showed a significant effect for the cyclization.展开更多
利用热重-微分热重技术研究了二炔丙基双酚A醚聚合物(PDPEBA)在氮气气氛中的非等温热分解过程,探讨了聚合物在不同升温速率下的热分解机理,并采用2种模型法和5种非模型法对二炔丙基双酚A醚聚合物热分解动力学三因子(E、A、f(a))进行计...利用热重-微分热重技术研究了二炔丙基双酚A醚聚合物(PDPEBA)在氮气气氛中的非等温热分解过程,探讨了聚合物在不同升温速率下的热分解机理,并采用2种模型法和5种非模型法对二炔丙基双酚A醚聚合物热分解动力学三因子(E、A、f(a))进行计算。结果表明,7种方法计算所得平均活化能及指前因子分别为E=176.30 k J/mol,lg A=10.43s-1;聚合物热分解阶段符合三维扩散机理,其对应的机理微分函数为f(α)=32(1-α)43×(1-α)-1[-3/1]-1,积分函数为g(α)=(1-α)-1[-3/1]2。展开更多
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 nuc...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.展开更多
以N,N′-二炔丙基苯胺和二甲基二氯硅烷为聚合单体,通过格式反应合成了含硅氮芳炔树脂,采用FTIR,1 H NMR表征其结构,利用DSC研究了含硅氮芳炔树脂的固化动力学,确定固化反应为一级反应,起始固化温度约为218℃。利用TGA分析了固化树脂的...以N,N′-二炔丙基苯胺和二甲基二氯硅烷为聚合单体,通过格式反应合成了含硅氮芳炔树脂,采用FTIR,1 H NMR表征其结构,利用DSC研究了含硅氮芳炔树脂的固化动力学,确定固化反应为一级反应,起始固化温度约为218℃。利用TGA分析了固化树脂的热性能,结果表明:含硅氮芳炔树脂在氮气中Td5为451℃,具有良好的耐热性。展开更多
文摘A highly efficient and selective[2+2+2]cyclization of diynes and monoalkynes was catalyzed by rhodium under room temperature in water/THF mixed solvent,affording isoindolines and isobenzofurans in good to excellent yields.The center atoms (N,O) in the diynes showed a significant effect for the cyclization.
文摘利用热重-微分热重技术研究了二炔丙基双酚A醚聚合物(PDPEBA)在氮气气氛中的非等温热分解过程,探讨了聚合物在不同升温速率下的热分解机理,并采用2种模型法和5种非模型法对二炔丙基双酚A醚聚合物热分解动力学三因子(E、A、f(a))进行计算。结果表明,7种方法计算所得平均活化能及指前因子分别为E=176.30 k J/mol,lg A=10.43s-1;聚合物热分解阶段符合三维扩散机理,其对应的机理微分函数为f(α)=32(1-α)43×(1-α)-1[-3/1]-1,积分函数为g(α)=(1-α)-1[-3/1]2。
基金Funded by the Financial Support of Shanghai Leading Academic Discipline Project(No.B502)Fundamental Research for the Central University
文摘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.
文摘以N,N′-二炔丙基苯胺和二甲基二氯硅烷为聚合单体,通过格式反应合成了含硅氮芳炔树脂,采用FTIR,1 H NMR表征其结构,利用DSC研究了含硅氮芳炔树脂的固化动力学,确定固化反应为一级反应,起始固化温度约为218℃。利用TGA分析了固化树脂的热性能,结果表明:含硅氮芳炔树脂在氮气中Td5为451℃,具有良好的耐热性。
