非等温法研究TGDDM/DDS体系固化反应动力学  

CURE KINETICS OF TGDDM/DDS SYSTEM STUDIED BY NON-ISOTHERMAL METHOD

作　　者：赵卫娟[1] 张佐光[1] 孙志杰[1] 张大兴[1] 

机构地区：[1]北京航空航天大学材料科学与工程学院,北京100083

出　　处：《高分子学报》2006年第4期564-568,共5页Acta Polymerica Sinica

基　　金：国家973项目(项目号2003CB615602);国家863项目(项目号2001AA335020)资助

摘　　要：采用DSC对4，4’-四缩水甘油基二氨基二苯基甲烷（TGDDM）和3，3＇-二氨基二苯基砜（DDs）体系的固化反应动力学进行了研究．分别通过n级反应法和Malek的最大概然机理函数法确定了固化反应机理函数，求解了固化反应动力学参数，得到了固化反应动力学模型．结果表明，通过Kissinger，Crane方法求解动力学参数所得到的n级反应模型与实验值差别较大；而采用Malek方法判别机理，表明该固化反应按照自催化反应机理进行，实验得到的DSC曲线与模型计算所得到的曲线吻合的较好，所确立的模型在5—20K／min的升温速率下能较好地描述TGDDM／DDS体系的固化反应过程，并为工艺参数的选择和工艺窗口的优化提供了理论依据．4,4＇-tetraglycidyldiaminodiphenyl methane （TGDDM） epoxy resins are widely used in the fields of aviation and airspace owing to their excellent properties, but the physical properties of the cured epoxy resins depend on their structure, the extent of cure, the curing conditions, the time and temperature of cure. So it is necessary to study the curing kinetics in order to obtain the optimal curing process. The Curing kinetics of TGDDM in presence of 3,3＇-diaminodiphenylsylfone （DDS） as the curing agent was studies by differential scanning calorimetry （DSC） technique at different heating rates. The kinetic mechanism functioin was determined using n order reaction and the most probability mechanism functioin method given by Malek respectively, the kinetic parameters of curing reaction were determined with the kinetic analysis of the data obtained by the thermal treatment, then the kinetic model was built. The results indicated that the n order model deduced from Kissinger and Crane equation, by which the parameters of curing reaction, the reaction order and activity energy were obtained, had great distinction with the experimental data. While the Malek analytical mechanism showed that the curing process of the curing reactions followed an autocatalytic reaction. The two-parameter （m, n ） autocatalytic model can well describe the curing reaction processs of the studied epoxy resins. The DSC curves obtained using the experimental data showed a good agreement with that theoretically calculated under 5 - 20 K/min heating rate. The research results will provide theoretical basis for the choice of manufacturing process and the optimization of processing window.

关 键 词：环氧树脂 固化反应 动力学模型 Malek法 DSC 

分 类 号：O643.1[理学—物理化学]