使用基于旋的Pd(II) α-二胺催化剂对乙烯与极性单体的共聚化进行机械研究
1Department of Chemistry, University of California, 1102 Natural Sciences 2, Irvine, California 92697, USA.
Journal of the American Chemical Society
|August 12, 2009
概括
这项研究揭示了一种带有环法连接体的类催化剂,可使乙烯和甲基烯酸盐 (MA) 在共聚物中高度结合. 这是因为连接体阻碍了单体交换,与标准催化剂不同.
科学领域:
- 有机金属化学 有机金属化学
- 聚合催化法 聚合催化法
- 机械学研究 机械学研究
背景情况:
- 之前的研究表明,烯酸盐与Pd (II) 旋催化剂的结合率很高.
- 标准的Pd(II) α-二胺催化剂在共聚合时表现出正常的柯廷-哈梅特动力学.
研究的目的:
- 通过Pd(II) 循环基α-二胺催化剂对乙烯/甲基烯酸盐 (MA) 共聚合进行详细的机械研究.
- 了解以前观察到异常高的MA纳入的原因.
主要方法:
- 研究了乙烯/MA共聚合动力学.
- 使用2D EXSY NMR和1H NMR光谱学研究了olefin交换率.
- 确定了olefin交换的平衡常数和激活障碍.
主要成果:
- 循环联体的轴阻断作用阻碍了氨酸的替代和平衡.
- 与非循环催化剂相比,乙烯的交换率是循环催化剂的100倍以上.
- 观察到高激活障碍的olefin交换,与迁移插入障碍可比.
结论:
- 由于循环联体的缓慢氨酸交换,可以防止前平衡.
- 这导致单体选择性降低,并且在乙烯/MA共聚合过程中具有较高的共聚体结合率.
- 催化剂设计为控制共聚合物组成提供了一个新的策略.
相关概念视频
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