【作者】 孙惠惠；

【导师】 黄丽；

【作者基本信息】 北京化工大学 ， 材料科学与工程， 2012， 硕士

【摘要】 环氧树脂是一种十分重要的传统材料,广泛应用胶黏剂、涂料以及复合材料等各个方面。但其阻燃性能差,限制了应用范围,因此,对其进行阻燃改性是研究的重点问题。由于磷元素阻燃效率高,且燃烧时放出的毒气少,对环境和人体友好,所以近年来得到了广泛的关注。本文旨在合成一种高磷含量的环氧树脂,可以将其作为阻燃剂添加到普通环氧树脂中使用。采用甲基膦酸二甲酯(DMMP)、乙二醇(EG)为原料,先合成出不同分子链长的端羟基膦酸酯中间体,然后使此中间体与环氧氯丙烷(ECH)反应,合成出含磷环氧树脂,并分别研究了它们对普通环氧树脂的阻燃性能和力学性能的影响。具体内容如下：利用DMMP和EG的酯交换缩聚反应,制得不同分子量的端羟基膦酸酯中间体,讨论了合成条件,并采用羟值滴定、红外(FTIR)、核磁(1H-NMR)方法表征了其结构。其中,反应条件为：合成温度为170-180℃,催化剂用量为原料总质量的1wt%,反应时间为5个小时。将第一步得到的三种中间体与环氧氯丙烷反应,经过一个两步反应制得含磷环氧树脂。讨论了合成条件,并采用环氧值滴定、红外(FTIR)、核磁(1H-NMR)方法表征了其结构。其中,反应条件为：催化剂三氟化硼乙醚的用量为0.6ml,氢氧化钠溶液的质量分数为40%。将合成产物添加到普通环氧树脂E-51中,考查了磷含量对树脂阻燃性和力学性能的影响,其中,当材料的磷含量为1.0%左右时,材料的极限氧指数都超过27.0,已成为阻燃材料,当磷含量为3.0%左右时,材料的极限氧指数最高可达32.0,阻燃效果优异；拉伸强度稍有降低,断裂伸长率提高。更多还原

【Abstract】 Epoxy resin is a very important traditional material, and is widely used inadhesives, coatings and conmposites. But epoxy has a poor flame retardant,which limites its application, so it is very important to improve this property.As phosphorus-containing compounds produce few harmful gases, and theyare much effective, so organic phosphorus is paid more attention.In this paper, a novel phosphorus-containing epoxy resin is synthesized, whichcan be mixed with other epoxy resins as flame retardant. DMMP and EG werefirst used to synthesize intermediate, then ECH was employed as rawmaterials to synthesize phosphorus-containing epoxy resin. With differentmolar ratio of EG/DMMP, three kinds of products were obtained. Theirinfluences to epoxy resin were investigated.Intermediate with different molecular weight were synthesized throughtransesterification of DMMP and EG. Synthetic technology was determined:temprature at170-180, the amount of catalyst was1wt%of the total massof raw materials, and the reaction time was5h. Structures of the intermediatewere confirmed by hydroxyl value titration, FTIR and1H-NMR.Three intermediate obtained in the first step were reacted with ECH to synthesize phosphorus-containing epoxy resin. Synthetic technology wasdetermined: the amount of catalyst was0.6ml, mass fraction of NaOH was40%, and temprature of ring-close reaction was30. Structures of productswere confirmed by epoxy value titration, FTIR and1H-NMR.The synthesized phosphorus-containing epoxy resin was mixed withepoxy resin E-51, LOI, tensile strength and elongation of cured products weretested. When phosphorus content was3%, LOI of32.0could be reached,while tensile strength reduced slightly, but elongation increased.更多还原