环氧树脂/超支化聚合物修饰碳纳米管复合材料的固化反应动力学研究

Study on Curing Kinetics of Epoxy Resin/Hyperbranched Polymer Modified Carbon Nanotubes Composites

采用非等温差示扫描量热法(DSC)研究纯环氧树脂(EP)、环氧树脂/碳纳米管复合材料(EP/MWCNTs)、环氧树脂/超支化聚酯修饰碳纳米管复合材料(EP/MWCNTs-H204)和环氧树脂/超支化聚酰胺修饰碳纳米管复合材料(EP/MWCNTs-N103)4种体系的固化动力学。基于Kissinger方法和Ozawa方法计算了各体系反应的活化能。结果表明:经过超支化聚合物修饰的EP/MWCNTs-H204和EP/MWCNTs-N103体系比未经修饰的其余两个体系,具有较低的表观活化能,说明超支化聚合物的引入对环氧树脂复合材料的固化反应具有显著的促进作用。采用Málek方法得出自动催化模型(Sesták-Berggren),利用Sesták-Berggren对各体系进行理论计算,提出了描述固化过程的动力学参数和方程式。理论计算结果与实验结果进行对比相似度较高,说明Sesták-Berggren模型可以很好地描述4种不同环氧树脂体系的固化动力学行为。

The curing kinetics of pure epoxy resin(EP),epoxy resin/carbon nanotubes composites(EP/MWCNTs),epoxy resin/hyperbranched polyester modified carbon nanotubes composites(EP/MWCNTs-H204) and epoxy resin/hyperbranched polyamide modified carbon nanotubes composites(EP/MWCNTs-N103) were studied by differential scanning calorimetry(DSC).The activation energy of each system was calculated based on Kissinger's method and Ozawa's method,respectively.The results show that the EP/MWCNTS-H204 and EP/MWCNTS-N103 systems modified by hyperbranched polymer have lower apparent activation energy than the other two systems without modification,which indicates that the introduction of hyperbranched polymer has a significant promotion on the curing reaction of epoxy resin composites.The automatic catalytic model(Sesták-Berggren) is obtained by Málek method.The kinetic parameters and equations describing the curing process are proposed by using Sesták-Berggren to theoretically calculate each system.The similarity between the theoretical calculation results and the experimental results is high,indicating that the SestákBerggren model can well describe the curing kinetic behavior of four different epoxy resin systems.