环开转化聚合物合成:基组的重要性
Scott C Radzinski1,2, Jeffrey C Foster1,2, Robert C Chapleski1
1Department of Chemistry, Virginia Tech , Blacksburg, Virginia 24061, United States.
Journal of the American Chemical Society
|May 25, 2016
概括
基组化学通过环开放转化聚合 (ROMP) 显著影响瓶聚合物合成. 精心选择基对于控制聚合动力学和实现高分子量 (MW) 瓶聚合物至关重要.
科学领域:
- 聚合物化学
- 材料科学
背景情况:
- 通过环开转化聚合物 (ROMP) 的瓶刷聚合物合成依赖于平衡聚合动力学和催化剂稳定性.
- 宏观分子 (MM) 基组化学是影响ROMP效率的关键因素.
研究的目的:
- 调查基化学对聚烯和聚乳酸宏观体的ROMP动力学的影响.
- 了解基组变异如何影响瓶聚合物分子重量和合成结果.
主要方法:
- 使用了Grubbs的第三代催化剂,用于不同基组的ROMP.
- 分析的聚合动力学,包括传播速度和最大可获得的分子量 (MW).
- 使用实验和计算研究来阐明群效应机制.
主要成果:
- 由于不同的群,不论是溶剂,MW或重复单元,传播速率的变化超过4倍.
- 增殖速度较慢的群将最大的瓶MW降低了一级.
- 添加三酸增加了传播速率,可能通过清除胺配体.
结论:
- 基组化学极大地影响了ROMP动力学和瓶聚合物的可实现分子量.
- 对于高MM转换和合成纯高MW瓶聚合物而言,合理的基选择至关重要.
- 观察到的速率差异归因于基组的固态和电子因子,而不是化.
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