Kinetic study and time‐temperature‐transformation cure diagram for an epoxy‐diamine system
Kinetic study and time‐temperature‐transformation cure diagram for an epoxy‐diamine system
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DOI：
10.1002/(sici)1097-4628(19971114)66:7
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发表时间：
1997-11
影响因子：
3
通讯作者：
L. Núñez;J. Taboada;F. Fraga;M. Nuñez
中科院分区：
文献类型：
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作者：
L. Núñez;J. Taboada;F. Fraga;M. Nuñez
研究了纯化的双酚 A 醚 (BADGE n = 0) 和 1,2-二胺环己烷 (DCH) 的固化反应中涉及的不同步骤，目的是计算该系统的时间-温度-转化 (TTT) 等温固化图。 Horie 等人提出的动力学模型。使用6并与实验数据进行比较。使用两种不同的方法测量胶凝时间和转化率：溶解度测试和动态机械分析（DMA）。两种方法获得的结果显示出合理的一致性。差示扫描量热法 (DSC) 数据显示 T g 和转化分数 α 之间存在一对一的关系，与固化温度无关。因此，T g 可以用作转化率的量度。使用模型参数以及 Tg 与转化率之间的关系，计算了 Tg 与 In 时间的关系，发现与 60 至 100°C 等温固化温度的 DSC 实验结果一致。通过将 T g 与 In 时间数据移动到参考温度 T r = 80°C，可以获得等温固化的动力学控制主曲线。表观活化能通过凝胶时间测量计算得出（溶解度测试中的 12.63 kcal mol -1 = 52.88 kJ mol -1 和 DMA 测量中的 12.28 kcal mol -1 = 51.42 kJ mol -1 ）。通过动力学模型的数值积分计算等转换轮廓。
The different steps involved in the curing reaction of a purified ether of bisphenol A (BADGE n = 0) and 1,2-diamine cyclohexane (DCH) were studied with the objective to calculate a time-temperature-transformation (TTT) isothermal cure diagram for this system. A kinetic model proposed by Horie et al. 6 was used and compared to the experimental data. Gelation times and conversions were measured using two different methods: solubility test and dynamic mechanical analysis (DMA). Results obtained by both methods show a reasonable agreement. Differential scanning calorimetry (DSC) data show a one-to-one relationship between T g and fractional conversion, α, independent of cure temperature. As a consequence, T g can be used as a measure of conversion. Using the model parameters and the relationship between T g and conversion, T g versus In time are calculated and found to agree with DSC experimental results for isothermal cure temperatures from 60 to 100°C. A kinetically controlled master curve for isothermal cure is obtained by shifting T g versus In time data to a reference temperature, T r = 80°C. The apparent activation energy was calculated from gel times measurements (12.63 kcal mol -1 = 52.88 kJ mol -1 from solubility test and 12.28 kcal mol -1 = 51.42 kJ mol -1 from DMA measurements). Isoconversion contours were calculated by numerical integration of the kinetic model.