含苯并噻唑链段耐热环氧树脂材料的制备及其固化动力学研究

Preparation and Curing Kinetics of Thermal Stable Epoxy Resin Material with Segment of Benzothiazole

基于4,5-环氧四氢邻苯二甲酸二缩水甘油酯(TDE-85)或N,N,N',N'-四缩水甘油基-4,4'-二氨基二苯基甲烷(AG-80)与2-氨基苯并噻唑(ABZ)的固化反应,以分阶段升温保温方式制备含刚性苯并噻唑链段的TDE-85/ABZ和AG-80/ABZ耐热环氧树脂材料.DMTA分析显示,TDE-85/ABZ和AG-80/ABZ固化物玻璃化转变温度分别为473 K和495 K.而TGA分析表明,其最大热降解速率对应温度分别为618 K和643 K,在873 K下仍有11%和13%的残余质量.以非等温DSC法研究TDE-85/ABZ和AG-80/ABZ固化反应动力学得出表观活化能分别为67.72 k J·mol-1和63.57 k J·mol-1,证明TDE-85/ABZ和AG-80/ABZ固化反应是以自催化反应机理进行的,动力学数学模型与DSC实验数据相吻合.这可为TDE-85/ABZ和AG-80/ABZ材料在成型加工工艺参数的优化和选择提供技术支撑.

Based on the curing reaction of 4,5-epoxycyclohexane-1,2-dicarboxylic acid diglycidyl ester（ TDE-85） or N,N,N＇,N＇-tetraglycidyl-4,4＇-diaminodiphenyl methane（ AG-80）with 2-aminobenzothiazole（ ABZ）,two kinds of thermal stable epoxy resin material containing the rigid segment of benzothiazole are prepared in a way of step raising and holding temperature. The DMTA analysis shows that the glass transition temperatures of TDE-85 / ABZ and AG-80 / ABZ are473 K and 495 K; moreover,the analysis of TGA shows that the temperatures corresponding to the fastest thermal degradation velocity of them under nitrogen are 618 K and 643 K and there are still11% and 13% residual mass at 873 K,respectively. The curing reaction kinetics of both TDE-85 /ABZ and AG-80 / ABZ systems is studied by non-isothermal DSC method and the results show that the apparent activation energy of the curing reactions are 67. 72 k J·mol- 1and 63. 57 k J·mol- 1,respectively. The curing reactions of both TDE-85 / ABZ and AG-80 / ABZ systems are confirmed by following autocatalytic reaction mechanisms. And the calculated curves of the kinetic mechanism functions fit experimental data well. The research results will provide technical support for the choice and optimization of manufacturing processes.