桐油聚酰亚胺酸酐/环氧固化体系动力学模型研究

Research of kinetic model of tung oil polyimide anhydride/epoxy curing system

通过示差扫描量热分析和热重分析以及力学性能测试研究了环氧树脂与自制的N,N-间苯撑双马来酰亚胺型桐油聚酰亚胺酸酐(HVAT酸酐)与N,N-4,4-二苯甲烷双马来酰亚胺型桐油聚酰亚胺酸酐(BMIT酸酐)固化体系的性能及固化反应动力学并与桐油酸酐/环氧固化体系作了对比。结果表明:3种体系的表观活化能分别为89.54,85.42和84.78kJ/mol,反应级数均为0.92,最优固化条件为100℃/2h+120℃/2h+150℃/1h。桐油聚酰亚胺酸酐/环氧固化体系的拉伸强度分别为36.42、38.60MPa,弯曲强度分别为57.19、46.68MPa,压缩强度分别为108.15、116.97MPa,剪切强度分别为13.73、15.57MPa,综合力学性能显著强于桐油酸酐/环氧固化体系。HVAT酸酐固化体系的Tg(99.60℃)和BMIT酸酐固化体系的Tg(91.96℃)显著高于桐油酸酐固化体系的Tg(57.63℃),初始热分解温度接近400℃。桐油聚酰亚胺酸酐固化体系具有更好的耐高温性。

The properties and curing kinetics of curing systems of epoxy resin and self-made N,N-m-phenylene bismaleimide type tung oil polyimide anhydride(HVAT anhydride)and N,N-4,4-diphenylmethane bismaleimide type tung oil polyimide anhydride(BMIT anhydride)were studied by differential scanning calorimetry and thermogravimetric analysis and mechanical properties test and compared with the tung oil anhydride/epoxy curing system. The results showed that the apparent activation energies of the three systems were 89.54,85.42 and 84.78 kJ/mol,respectively,and the reaction order is 0.92. The optimal curing condition was 100 ℃/2 h + 120 ℃/2 h + 150 ℃/1 h. The tensile strengths of tung oil polyimide anhydride/epoxy curing system were 36.42 and 38.60 MPa,respectively. The flexural strengths were 57.19 and 46.68 MPa,respectively. The compressive strengths were 108.15 and 116.97 MPa,respectively. The shear strengths were 13.73 and 15.57 MPa,respectively. The comprehensive mechanical properties were significantly stronger than those of tung oil anhydride/epoxy curing system. The Tgof the HVAT anhydride curing system(99.60 ℃) and the Tgof the BMIT anhydride curing system(91.96 ℃)were significantly higher than the Tgof the tung oil anhydride curing system(57.63 ℃),and the initial thermal decomposition temperature was close to 400 ℃. The tung oil polyimide anhydride curing system had better high temperature resistance.