大量的类基清除剂在烯酸聚合物与4组催化剂的聚合
Russell A Stapleton1, Brandon R Galan, Scott Collins
1Department of Polymer Science, University of Akron, Akron, Ohio 44325, USA.
Journal of the American Chemical Society
|August 2, 2003
概括
水与甲基氨酸复合物反应,形成一个不稳定的水复合物. 这种复合物分解,由此产生的受阻醇对烯聚合动力学对烯催化剂的作用最小.
科学领域:
- 有机金属化学 有机金属化学
- 催化剂是一种催化剂.
- 聚合物科学 聚合物科学
背景情况:
- 甲基氨酸 (MAO) 是olefin聚合的关键联合催化剂.
- 了解MAO的反应性及其与蛋白质物种的相互作用对于催化剂设计至关重要.
- conocene复合物被广泛用作聚烯生产中的催化剂.
研究的目的:
- 为了研究水与硬质阻碍的甲基氨酸复合物的反应.
- 描述由此产生的水族复合物及其分解途径.
- 为了评估分解产品 - - 一种受阻的 - - 对基催化烯聚合物的影响.
主要方法:
- 使用X射线晶体学合成和结构性表征水族复合物.
- 对水族复合物分解的动力学研究.
- 阻碍和conocene催化剂之间的反应的动力学研究.
- 在受阻醇的存在下监测聚合的对照实验.
主要成果:
- 形成和X射线结晶结构的确定水族复合物[MeAl(OAr) 2 ((H2O) ] (2).
- 复合物2在0°C以上分解,产生受阻的 (ArOH),甲和甲基.
- 分解遵循第一阶动力学 (k = 3.0 x 10−4 s−1 在5°C).
- 阻断的醇与[Cp2ZrMe][MeB(C6F5) 3] (4) (k = 2.8 x 10−3 M−1s−1 在25°C) 反应缓慢.
- 这种反应速度比催化剂4的乙烯插入速度慢107倍以上.
- 添加ArOH并没有影响聚乙烯形成动力学.
结论:
- 这种水族复合体不稳定,很容易分解.
- 被阻碍的二醇副产品并没有显著抑制可诺催化剂在烯聚合中的活性.
- 这些发现表明,在聚合条件下,conocene 催化剂对蛋白质杂质的强度很高.
相关概念视频
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