环氧-酚醛-双马来酰亚胺三元共混物的制备及性能研究

Preparation and properties of epoxy-phenolic aldehyde-bismaleimide ternary blend

采用4,4′-二苯甲烷双马来酰亚胺(BMI)与多芳环型酚醛树脂、多芳环型环氧树脂(NC3000)及促进剂2-苯基-4-甲基-5-羟甲基咪唑(2P4 MHZ)熔融共混,制备了三元树脂共混物(BPE)及其固化产物,并对其性能进行了评价。研究结果表明:BPE三元树脂共混物仅出现了一种固化行为,在现有环氧塑封料(EMC)制备工艺中可固化完全;结构特征分析表明,成功制备了BPE三元树脂共混物,并且三元树脂之间发生了相互交联反应;三元树脂共混物的结晶状态及流变学分析表明,三元共混物呈现出明显的非晶特性,随着温度的升高,熔体黏度均开始下降,在140~160℃时达到最低值,然后随着凝胶化会迅速增加几个数量级,并且在110~160℃内存在一定的加工窗口,对EMC的制备是有利的;随着BMI含量的增加,三元树脂固化物的耐热稳定性也在不断增加,10%的热分解温度均超过430℃;此外,BMI引入也使得共混物凝胶时间延长,并且破坏了环氧/酚醛树脂体系的固化交联,导致高温热老化失重的增多。

A ternary resin blend(BPE)and its cured product were prepared by melt blending 4,4′-diphenylmethane bismaleimide(BMI)with polyaromatic ring phenolic resin,polyaromatic ring epoxy resin(NC3000),and promoter 2-phenyl-4-methyl-5-hydroxymethylimidazole(2P4 MHZ),and their properties were evaluated.The research results showed that the BPE ternary resin blend only exhibited one curing behavior,which could be fully cured in the existing epoxy molding compound(EMC)preparation process.Structural characteristic analysis showed that the BPE ternary resin blend had been successfully prepared,and mutual crosslinking reactions had occurred between the ternary resins.The crystalline state and rheological analysis of the ternary resin blend showed that the ternary resin blend exhibited obvious amorphous characteristics.With the increase of temperature,the melt viscosity began to decline,reaching the lowest value at 140-160℃,and then rapidly increased several orders of magnitude with gelation,and there existed a certain processing window at 110-160℃,which was beneficial to the preparation of EMC.With the increase of BMI content,the heat resistance stability of the cured ternary resin was also constantly increasing,and the thermal decomposition temperature of 10% exceeded 430℃.In addition,the introduction of BMI also prolonged the gelation time of the blend,and destroyed the curing and crosslinking of the epoxy/phenolic aldehyde resin system,resulting in increased weight loss during high-temperature thermal aging.