功能化纳米SiO2-聚醚砜/BMI-酚醛环氧树脂复合材料的固化动力学与性能
Curing reaction kinetics and properties of functionalized nano SiO2-polyethersulfone/BMI- phenolic epoxy resin composites

以4，4’-二氨基二苯甲烷（DDM）为固化剂、双马来酰亚胺（BMI）和酚醛环氧树脂（F51）为基体、聚醚砜（PES）为增韧剂、硅烷偶联剂KH560功能化纳米SiO2（KH-SiO2）为改性剂，采用原位聚合法制备了KH-SiO2-PES/BMI-F51复合材料，并通过非等温DSC确定了复合材料的固化工艺及固化反应动力学。根据Kissinger方程和Ozawa方程求得体系的表观活化能分别为96.03 kJ/mol和99.18 kJ/mol。FTIR测试结果表明：KH-SiO2改性效果良好，不饱和双键和环氧基特征峰消失，BMI中C=C双键和F51中环氧基在DDM作用下参与了体系的固化反应。SEM结果表明：PES树脂和KH-SiO2含量适当时，PES树脂和KH-SiO2在树脂基体中分散均匀，断裂纹不规则杂乱发展，KH-SiO2-PES/BMI-F51复合材料呈韧性断裂。力学性能测试和热失重测试表明：当PES含量为4wt%，KH-SiO2含量为1.5wt%时，KH-SiO2-PES/BMI-F51复合材料的弯曲强度、弯曲模量和冲击强度分别为156.23 MPa、4.18 GPa和20.89 kJ/m2，较BMI-F51基体分别提高了49.7%、29.4%和82.8%；KH-SiO2-PES/BMI-F51复合材料的热分解温度为393.1℃，残重率为50%时，分解温度高达523.1℃，耐热性十分优异。KH-SiO2-PES/BMI-F51复合材料的力学性能和耐热性有了较大提高，为拓展F51及BMI的应用范围提供了一定的理论数据。 With 4,4'-diamino diphenyl methane (DDM) as the curing agent, bismaleimide (BMI) and phenolic epoxy resin (F51) as the matrix, polyethersulfone (PES) as the toughening agent and functionalized nano SiO2 by silane coupling agent KH560(KH-SiO2) as the modifier, the KH-SiO2-PES/BMI-F51 composites were prepared by in-situ polymerization method, and the curing process and reaction curing kinetics were determined by non-isothermal DSC. The apparent activation energy of KH-SiO2-PES/BMI-F51 composites are 96.03 kJ/mol and 99.18 kJ/mol according to Kissinger equation and Ozawa equation, respectively. The FTIR results reveal that the surface modification of KH-SiO2 is favourable, the characteristic peaks of unsaturated double bond and epoxy group disappear, and the C=C double bond in BMI and epoxy group in F51 are involved in the curing reaction of KH-SiO2-PES/BMI-F51 composites under the effect of DDM. The SEM images exhibit that PES resin and KH-SiO2 uniformly disperse in the resin matrix when the content of PES resin and KH-SiO2 are appropriate, the broken cracks develop irregularly and the material exhibits ductile fracture. The mechanical performances and thermogravimetric properties show that bending strength, bending modulus and impact strength of KH-SiO2-PES/BMI-F51composites are 156.23 MPa, 4.18 GPa and 20.89 kJ/m2, when the mass fraction of PES and KH-SiO2 are 4wt% and 1.5wt%, which are 49.7%, 29.4% and 82.8% higher than that of BMI-F51 matrix, respectively. The thermal decomposition temperature of KH-SiO2-PES/BMI-F51 composites is 393.1℃, and the temperature at the residual mass of 50% reaches 523.1℃, the heat-resistant property is excellent. The mechanical properties and heat-resistant properties of KH-SiO2-PES/BMI-F51 composites are greatly improved, which provides theoretical data for expanding the application range of F51 and BMI. 国家自然科学基金（21604019）；哈尔滨创新人才专项（2015RAXXJ029