氨基化ZIF-67协同改性环氧树脂阻燃材料的热解特性

Thermal decomposition characteristics of amino modified ZIF-67 synergistic modified epoxy resin flame retardant material

  • 摘要: 对环氧树脂(EP)材料进行热解动力学研究,是连接基础材料性能与终端工业应用的桥梁。本工作使用氨基功能化沸石咪唑酯骨架材料(NH2-ZIF-67)协同三聚氰胺聚磷酸盐(MPP)和含磷低分子聚苯醚(MPPO)对EP进行改性,制备EP阻燃材料。通过多等转化率无模型法联用并构建Coats-Redfern-主曲线法分析EP阻燃材料的热解动力学。结果表明:随着阻燃剂的引入,EP阻燃材料的活化能(Ea)和指前因子(A)都低于纯EP;其中1wt%NH2-ZIF-67的加入使得阻燃材料的Ea降为48.78±2.37 kJ/mol,材料的热解行为更容易发生,这是因为EP阻燃材料中的MPP、NH2-ZIF-67材料具有催化成炭作用,且多组分材料在热解中互相协同作用,进而导致热解反应加速。根据Coats-Redfern与主曲线法对常见机理函数进行分析,其中实验曲线与标准曲线最契合F2、F3机理模型,EP阻燃材料热解行为可以被随机成核反应定量描述。

     

    Abstract: The study on the pyrolysis kinetics of epoxy resin (EP) materials serves as a bridge connecting the performance of basic materials and terminal industrial applications. In this work, amino functionalized zeolite imidazole ester skeleton material (NH2-ZIF-67), melamine polyphosphate (MPP) and phosphorus containing low molecular polyphenylene oxide (MPPO) were employed to modify EP to prepare EP flame retardant materials. The pyrolysis kinetics of EP flame-retardant materials was analyzed by combining multiple iso-conversional model-free methods and using the constructed Coats-Redfern-master plot method. The results showed that with the incorporation of flame retardant, both the activation energy (Ea) and pre-exponential factor (A) of the EP flame retardant materials were lower than those of pure EP. The addition of 1wt% NH2-ZIF-67 reduced the Ea of flame retardant materials to 48.78±2.37 kJ/mol, and the pyrolysis behavior of materials was more prone to occur. This was because MPP and NH2-ZIF-67 materials in EP flame retardant materials had catalytic charring effect, and multi-component materials cooperated with each other in the pyrolysis process, which led to the acceleration of pyrolysis reaction. Common mechanism functions were analyzed according to Coats-Redfern and master plot method. The experimental curve and standard curve were the most consistent with F2 and F3 mechanism models. The pyrolysis behavior of EP flame retardant materials could be quantitatively described by random nucleation reaction.

     

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