海因环氧树脂的合成及其与六氢苯酐的固化行为

目的研究海因环氧树脂的固化行为,为绿色环保水性涂层和表面粘接剂的开发与研制提供一定的基础数据和理论指导。方法合成了一种新型海因环氧树脂,以六氢苯酐(HHPA)为固化剂,制备了海因环氧/HHPA树脂体系。采用差示扫描量热法研究其在不同升温速率下的固化行为,通过Melak等效转换公式及双参数(m,n)自催化模型,分别确定海因环氧/HHPA树脂体系的固化反应机理函数和相关动力学参数,得到固化反应动力学方程。结果所制备的新型海因环氧值为0.65当量,无机氯含量为0.000 673当量,有机氯含量为0.0274当量。通过Ozawa-Flynn-Wall法和Friedman-Reich-Levi法确定了海因环氧树脂/HHPA体系的表观活化能分别为82.2、83.7 k J/mol,通过malek方程计算得到树脂体系的反应级数n=1.531,m=0.68,指前因子A=1.75×10¹⁰。所建立的固化动力学方程为βdα/dT=1.75×10¹⁰α^0.68(1-α)^1.531expa(-Eα/RT)。结论海因环氧树脂/HHPA固化反应按照自催化反应机理进行,并建立了海因环氧树脂的固化反应动力学模型。所确立的固化反应动力学模型计算得到的曲线与实验得到的DSC曲线吻合较好,在该研究范围内能较好地描述海因环氧树脂/HHPA体系的固化反应过程。

Curing Kinetic of Hydantoin Epoxy/HHPA System by Non-isothermal Data

The work aims to provide some basic data and theoretical guidance for the development and research of green water-based coating and surface adhesive based on the research in the curing behavior of hydantoin epoxy resin. A new type of hydantoin epoxy resin was synthesized, and hydantoin epoxy resin/HHPA resin was prepared by using hexahydrophthalic anhydride (HHPA) as curing agent. The curing behavior under different heating rates was studied by differential scanning calorimetry (DSC). The mechanism of curing reaction of hydantoin epoxy resin/HHPA resin system was determined by Melak equivalent conversion equation and two-parameter (m, n) autocatalytic model respectively. The curing reaction kinetics equation was got by related kinetic parameters. The new epoxy was prepared with the epoxy value of 0.65, the inorganic chlorine content of 0.000 673 eq and the organic chlorine content of 0.0274 eq respectively. The apparent activation energies of hydantoin epoxy resin/HHPA system were 82.2 kJ/mol and 83.7 kJ/mol, respectively. Ozawa-Flynn-Wall method and Friedman-Reich-Levi method were used to calculate the resin system reaction Series, n=1.531, m=0.68, before the factor A=1.75×1010, the established the curing kinetics equation was. The curing reaction of hydantoin epoxy resin/HHPA was carried out according to the autocatalytic reaction mechanism. The kinetic model of curing reaction of hydantoin epoxy resin was established. The established curve of the curing reaction kinetics model is in good agreement with the experimental DSC curve. The curing reaction process of the epoxy resin/HHPA system can be well described within the scope of this study.