从4,4'-Methylenediphenyl Diisocyanate中形成聚碳二胺的动力学和机械学研究
Marcell D Csécsi1,2, R Zsanett Boros3, Péter Tóth3
1Institute of Chemistry, University of Miskolc, Miskolc-Egyetemváros, H-3515 Miskolc, Hungary.
这项研究研究了聚氨生产中从4,4'-甲基二二酸盐 (MDI) 形成碳二胺的过程. 分析了反应动力学,揭示了初始二阶行为和60.4kJ/mol的激活能量.
科学领域:
- 聚合物化学 聚合物化学
- 有机合成 有机合成
- 化学动力学 化学动力学
背景情况:
- 碳二胺在通过与异酸盐反应来改变聚氨特性方面至关重要.
- 4,4'-甲基二二酸 (MDI) 是聚氨行业的一个关键原料.
- 了解从MDI中碳胺形成的动力学对于过程优化至关重要.
研究的目的:
- 从MDI中动态研究双功能碳二胺的形成.
- 为了从MDI中确定碳胺合成的反应顺序和激活能量.
- 用过渡状态理论将实验结果与理论预测进行比较.
主要方法:
- 使用气体体积测量来监测CO2在50-80°C的演变的实验动力学研究.
- 使用3 - 甲基-1--2-烯-1-氧化物 (MPPO) 在正二二 (ODCB) 中的催化工艺.
- 在过渡状态理论 (TST) 中使用DFT和IRC计算的计算分析.
主要成果:
- 最初的反应阶段表现出二次动力学,速度常数取决于温度.
- 由于寡合体形成和副作用,观察到偏离第二阶动力学.
- 激活能被确定为60.4 ± 3.0 kJ/mol,在理论和实验方法中一致.
结论:
- 碳胺键形成的激活能量独立于MDI中异酸盐群的数量和位置.
- 对于这种碳胺形成反应,函数组的同等反应性原则是正确的.
- 这些发现为控制聚氨合成中的碳二胺形成提供了有价值的动力学数据.
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