烯丙基醚化酚醛亚胺树脂的固化动力学研究

Study on curing kinetics of allyl etherified phenolic imine resin

采用差示扫描量热仪测定了不同升温速率下烯丙基醚化酚醛亚胺树脂(APMI-F树脂)的DSC曲线,用非等温热力学的研究方法研究了APMI-F树脂的固化反应动力学。用T-β外推法确定了APMI-F树脂的固化反应的起始温度Ti、峰值温度Tp和终止温度Tf,并将其作为探究APMI-F树脂固化工艺的依据。通过Kissinger法和Starink法求得APMI-F树脂的表观活化能,由Starink法得到不同固化度下的表观活化能,并将其与试验数据对比,以验证固化动力学模型的准确性。研究结果表明:(1)利用外推法确定了APMI-F树脂固化反应的Ti、Tp和Tf分别为161.09、226.81、263.42℃;(2)Starink法求得的平均活化能要高于Kissinger法所得数据;(3)在固化反应过程中,随着固化程度的升高,APMI-F树脂的表观活化能呈现先降低后升高的趋势,固化初期活化能因黏度的降低而降低,随着交联度的提高,链段运动受到限制导致活化能渐渐升高;(4)采用Málek法成功地建立了APMI-F树脂的固化动力学模型,通过与试验数据对比,发现该模型能够很好地描述APMI-F树脂的固化过程。

The DSC curves of allyl etherified phenolic imine resin(APMI-F resin) were measured at different heating rates by using differential scanning calorimeter.The curing reaction kinetics of APMI-F resin were studied by using non isothermal thermodynamic research method.Using T-β extrapolation method,the starting temperature Ti,peak temperature Tp,and termination temperature Tf of the curing reaction of APMI-F resin were determined,and it was used as the basis for exploring the curing process of APMI-F resin.The apparent activation energy of APMI-F resin was obtained by Kissinger method and Starink method.The apparent activation energy at different curing degrees was obtained by Starink method and compared with experimental data to verify the accuracy of the curing kinetics model.The research results showed that,(1) The Ti,Tp and Tf of the curing reaction of APMIF resin were determined by extrapolation method to be 161.09,226.81 and 263.42 ℃,respectively.(2) The average activation energy obtained by Starink method was higher than that obtained by Kissinger method.(3) During the curing reaction,as the degree of curing increased,the apparent activation energy of APMI-F resin showed a trend of first decreasing and then increasing.In the initial stage of curing,the activation energy decreased due to the decrease in viscosity.As the degree of crosslinking increased,the movement of chain segments was limited,leading to a gradual increase in activation energy.(4) The curing kinetics model of APMI-F resin was successfully established through the Málek method,and compared with experimental data,it was found that the model could well describe the curing process of APMI-F resin.