双酚A型环氧树脂/芳香胺固化体系的固化动力学研究

Study on curing kinetics of bisphenol A epoxy resin/aromatic amine curing system

分别以4,4'-二氨基二苯甲烷(DDM)和4,4'-二氨基二苯砜(DDS)为固化剂,采用非等温差示扫描量热法(DSC)研究了E-44和E-51两种双酚A型环氧树脂的固化反应动力学。收集与分析了在25~350℃范围内分别以5、10、15、20℃/min的升温速率进行固化的反应参数,然后采用Starink法计算得到不同环氧固化体系的表观活化能。同时,借助各固化体系的动态流变性能,分析了双酚A型环氧树脂/芳香胺固化体系的固化反应机理,并选用双参数自催化模型计算了各固化体系的反应速率方程。研究结果表明:当环氧固化体系的固化剂不同时,采用DDM作为固化剂的环氧固化体系(E-44/DDM、E-51/DDM),其表观活化能均低于添加DDS固化剂的环氧体系;选用同种固化剂(DDM或DDS)时,E-51树脂体系的表观活化能均低于E-44树脂固化体系。反应速率方程结果显示,该双参数自催化模型与实际试验结果的吻合性良好,可用于描述双酚A型环氧树脂/芳香胺固化体系的固化历程。

Using 4,4’-diaminodiphenyl methane(DDM)and 4,4’-diaminodiphenyl sulfone(DDS)as curing agent,the curing kinetics of two kinds of bisphenol A epoxy resin,i.e.E-44 and E-51,were studied by nonisothermal differential scanning calorimetry(DSC).The reaction parameters of curing at 5,10,15 and 20℃/min in the temperature range of 25-350℃were collected and analyzed,and then the apparent activation energies of different epoxy curing systems were calculated by Starink method.At the same time,the curing reaction mechanism of bisphenol A epoxy resin/aromatic amine curing system was analyzed by using the dynamic rheological properties of each curing system,and the reaction rate equation of each curing system was calculated by using the twoparameter autocatalytic model.The research results showed that when the curing agent of epoxy curing system was different,the apparent activation energies of epoxy curing systems with DDM as curing agent(E-44/DDM,E-51/DDM)were lower than those of epoxy systems with DDS curing agent.When the same curing agent(DDM or DDS)was selected,the apparent activation energy of E-51 resin system was lower than that of E-44 resin curing system.The reaction rate equation results showed that the two-parameter autocatalytic model was in good agreement with the actual test results,which could be used to describe the curing process of bisphenol A epoxy resin/aromatic amine curing system.