Al2O3/环氧树脂-氰酸酯复合材料反应动力学及力学性能  

Reaction kinetics and mechanical properties of Al2O3/epoxy-cyanate ester composites

作　　者：陈宇飞[1,2] 李治国 刘宇龙 滕成君[3] 崔巍巍[1] CHEN Yufei;LI Zhiguo;LIU Yulong;TENG Chengjun;CUI Weiwei(School of Materials Science and Engineering,Harbin University of Science and Technology,Harbin 150040,China;Key Laboratory of Engineering Dielectrics and its Application,Ministry of Education,Harbin University of Science and Technology,Harbin 150080,China;Harbin Xiangfang District Center for Disease Control and Prevention,Harbin 150030,China)

机构地区：[1]哈尔滨理工大学材料科学与工程学院,哈尔滨150040 [2]哈尔滨理工大学工程电介质及应用技术教育部重点实验室,哈尔滨150080 [3]哈尔滨市香坊区疾病预防控制中心,哈尔滨150030

出　　处：《复合材料学报》2020年第4期749-757,共9页Acta Materiae Compositae Sinica

基　　金：国家自然科学基金(51177030);哈尔滨创新人才专项(2015RAXXJ029)。

摘　　要：以双酚A型环氧树脂(E51)和双酚A型氰酸酯(BCE)为原料,研究E51改性BCE共固化反应机制。同时,以E51-BCE为基体树脂,溶胶-凝胶法(Sol-Gel)自制Al2O3为增强体,制备Al2O3改性E51-BCE (Al2O3/E51-BCE)复合材料。通过非等温DSC确定了E51-BCE体系的固化工艺及固化反应动力学,并根据Kissinger法和Ozawa法求得体系的表观活化能分别为66.13 kJ/mol和69.46 kJ/mol。利用红外光谱跟踪固化体系在起始固化温度为160℃、 180℃时的反应历程,结果表明:起始固化温度在160℃时,以E51与BCE直接反应为主;起始固化温度在180℃时, BCE反应活性提高,以BCE自聚反应为主,生成三嗪环的速率加快,少量的BCE直接与E51反应生成恶唑啉结构。对Sol-Gel法自制Al2O3进行FTIR和TEM表征,结果表明:Al2O3为短纤维状的晶体,表面含有少量羟基。SEM结果显示:Al2O3为分散相,与基体间界面模糊, Al2O3/E51-BCE复合材料的脆断面裂纹不规则,为典型的韧性断裂;当Al2O3掺杂量为3wt%时, Al2O3在基体中分散均匀, Al2O3/E51-BCE复合材料的冲击强度和弯曲模量分别为24.2 kJ/m2和2.54 GPa,比基体树脂的冲击强度和弯曲模量分别提高53.65%和22.12%,力学性能得到明显改善。The bisphenol A epoxy resin(E51) and bisphenol A cyanate(BCE) were used as the raw materials to study the co-curing reaction kinetics mechanism. At the same time, E51-BCE was used as the matrix resin, and Al2O3 obtained with Sol-Gel method as reinforcement to prepare the Al2O3/E51-BCE composites. The solidification process and curing kinetics of the system were determined by non-isothermal DSC, and the apparent activation energy of the system are 66.13 kJ/mol and 69.46 kJ/mol according to the Kissinger and Ozawa equation, respectively. Infrared spectroscopy was used to track the reaction route of the system at the initial curing temperature of 160℃ and 180℃. The results reveal that E51 reacts directly with BCE when the curing temperature starts at 160℃. The BCE’s reactivity will be improved when the curing temperature is 180℃, BCE is mainly consumed in the self-polymerization reaction, and the formation rate of the triazine ring is accelerated. A little part of BCE directly reacts with E51 to form an oxazoline structure. The FTIR and TEM results of Al2O3 show that the structure of Al2O3 is a short fiber-like crystal with a little amount of hydroxyl groups on its surface. The SEM patterns of the Al2O3/E51-BCE composites indicate that Al2O3 presents as disperse phase in matrix, the interface between Al2O3 and matrix is fuzzy and the failure cracks are irregularity, thus it is typical ductile fracture. 3 wt% Al2O3 is uniformly dispersed in matrix, and the impact strength and bending modulus of Al2O3/E51-BCE composites is 24.2 kJ/m2 and 2.54 GPa, respectively, which are increased by 53.65% and 22.12% compared with E51-BCE matrix resin. The mechanical properties of Al2O3/E51-BCE composites are improved obviously.

关 键 词：双酚A型氰酸酯 环氧树脂 反应机制 反应动力学 力学性能 

分 类 号：TB332[一般工业技术—材料科学与工程]