芳香胺固化环氧树脂非等温DSC动力学的研究

摘要

Based on the data obtained by the non-isothermal DSC tests,the reaction kinetics of curing of bisphenol-A epoxy resin with aromatic amine were investigated by using the phenomenological model method and the model-free method.In the phenomenological model method,we forecasted the curing system according with the SB double parameter autocatalytic model by employing the M á lek method.To reduce fitting errors,the dynamic modification factor Cf was introduced to revise the fitting obtained by using the least square fitting based on Levenberg-Marquardt (LM) algorithm.For the model-free method,using the improved isoconversional method (NLV method) the values of activation energy (Eα) at different curing degree(α) were obtained,and the compensation parameters were obtained through the ABS differential method for several simplified SB equations.The results show that by introducing the modification factor Cf,the SB double parameters autocatalytic model can better fit the kinetic process of curing reaction of the curing system.At the early stage of reaction,the Eα value falls off fast as α increased.But at the later period of reaction,the Eα value was gradually increased.In addition,the relationship between activation energy (Eα) and pre-exponential factor (A) can be expressed by the compensation parameter equation better.%基于非等温DSC得到的数据,采用唯像模型法及非模型法研究了环氧树脂/芳香胺固化体系的固化动力学.唯像模型法中,通过对固化曲线及Málek法引入的y(α),z(α)曲线分析,预测了该固化体系符合SB双参数自催化模型,并使用Levenberg-Marquardt (LM)算法进行最小二乘拟合,引入动力学修正因子Cf进行修正拟合;非模型法中,使用改进的等转化率法(NLVVyazovkin法)计算了不同固化度(α)条件下活化能(Eα)的大小,通过ABS微分法对几组简化的SB方程进行了补偿参数计算.结果表明,引入Cf的SB双参数自催化模型能够较好地拟合该固化体系固化反应动力学过程;反应前期Eα随α增加而快速下降,固化反应后期Eq又逐渐增加;Eα与指前因子(A)之间的关系能够通过“补偿参数”方程进行较好的表达.